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Property System

Version Number: V7.1

January 2009

Copyright (c) 1981-2009 by Aspen Technology, Inc. All rights reserved.

Aspen Physical Property System, the aspen leaf logo and Plantelligence and Enterprise Optimization are trademarks

or registered trademarks of Aspen Technology, Inc., Burlington, MA.

All other brand and product names are trademarks or registered trademarks of their respective companies.

This document is intended as a guide to using AspenTech's software. This documentation contains AspenTech

proprietary and confidential information and may not be disclosed, used, or copied without the prior consent of

AspenTech or as set forth in the applicable license agreement. Users are solely responsible for the proper use of

the software and the application of the results obtained.

Although AspenTech has tested the software and reviewed the documentation, the sole warranty for the software

may be found in the applicable license agreement between AspenTech and the user. ASPENTECH MAKES NO

WARRANTY OR REPRESENTATION, EITHER EXPRESSED OR IMPLIED, WITH RESPECT TO THIS DOCUMENTATION,

ITS QUALITY, PERFORMANCE, MERCHANTABILITY, OR FITNESS FOR A PARTICULAR PURPOSE.

200 Wheeler Road

Burlington, MA 01803-5501

USA

Phone: (1) (781) 221-6400

Toll Free: (1) (888) 996-7100

URL: http://www.aspentech.com

Contents

1 Introduction .........................................................................................................5

Units for Temperature-Dependent Parameters .................................................... 6

Pure Component Temperature-Dependent Properties .......................................... 7

Extrapolation Methods .................................................................................... 9

Equation-of-State Models ...............................................................................14

ASME Steam Tables .............................................................................15

BWR-Lee-Starling................................................................................16

Benedict-Webb-Rubin-Starling ..............................................................17

Hayden-O'Connell................................................................................20

HF Equation-of-State ...........................................................................22

Ideal Gas ...........................................................................................26

Lee-Kesler..........................................................................................26

Lee-Kesler-Plöcker...............................................................................28

NBS/NRC Steam Tables........................................................................29

Nothnagel ..........................................................................................30

Copolymer PC-SAFT EOS Model .............................................................32

Peng-Robinson....................................................................................44

Standard Peng-Robinson ......................................................................46

Peng-Robinson-MHV2 ..........................................................................48

Predictive SRK (PSRK) .........................................................................48

Peng-Robinson-Wong-Sandler ...............................................................48

Redlich-Kwong ....................................................................................49

Redlich-Kwong-Aspen ..........................................................................49

Redlich-Kwong-Soave ..........................................................................50

Redlich-Kwong-Soave-Boston-Mathias....................................................52

Redlich-Kwong-Soave-Wong-Sandler .....................................................54

Redlich-Kwong-Soave-MHV2 .................................................................54

Schwartzentruber-Renon ......................................................................54

Soave-Redlich-Kwong ..........................................................................56

SRK-Kabadi-Danner.............................................................................58

SRK-ML .............................................................................................60

VPA/IK-CAPE Equation-of-State.............................................................61

Peng-Robinson Alpha Functions .............................................................66

Huron-Vidal Mixing Rules......................................................................76

MHV2 Mixing Rules ..............................................................................78

Predictive Soave-Redlich-Kwong-Gmehling Mixing Rules ...........................79

Wong-Sandler Mixing Rules ..................................................................81

Activity Coefficient Models ..............................................................................83

Bromley-Pitzer Activity Coefficient Model ................................................83

Chien-Null ..........................................................................................86

Contents 1

Constant Activity Coefficient .................................................................88

COSMO-SAC .......................................................................................88

Electrolyte NRTL Activity Coefficient Model ..............................................91

ENRTL-SAC ...................................................................................... 104

Hansen ............................................................................................ 109

Ideal Liquid ...................................................................................... 110

NRTL (Non-Random Two-Liquid).......................................................... 110

NRTL-SAC Model ............................................................................... 112

Pitzer Activity Coefficient Model ........................................................... 122

Polynomial Activity Coefficient............................................................. 133

Redlich-Kister ................................................................................... 135

Scatchard-Hildebrand ........................................................................ 135

Three-Suffix Margules ........................................................................ 136

UNIFAC Activity Coefficient Model ........................................................ 137

UNIFAC (Dortmund Modified) .............................................................. 139

UNIFAC (Lyngby Modified) .................................................................. 140

UNIQUAC Activity Coefficient Model ..................................................... 141

Van Laar Activity Coefficient Model ...................................................... 143

Wagner Interaction Parameter ............................................................ 144

Wilson Activity Coefficient Model.......................................................... 145

Wilson Model with Liquid Molar Volume................................................. 146

Vapor Pressure and Liquid Fugacity Models ..................................................... 147

Extended Antoine/Wagner/PPDS/IK-CAPE Liquid Vapor Pressure Model ..... 147

API Sour Model ................................................................................. 152

Braun K-10 Model ............................................................................. 152

Chao-Seader Pure Component Liquid Fugacity Model .............................. 153

Grayson-Streed Pure Component Liquid Fugacity Model .......................... 153

Kent-Eisenberg Liquid Fugacity Model................................................... 154

Maxwell-Bonnell Vapor Pressure Model ................................................. 155

Solid Antoine Vapor Pressure Model ..................................................... 155

DIPPR/Watson/PPDS/IK-CAPE Heat of Vaporization Model ................................. 156

DIPPR Heat of Vaporization Equation.................................................... 156

Watson Heat of Vaporization Equation .................................................. 157

PPDS Heat of Vaporization Equation ..................................................... 157

IK-CAPE Heat of Vaporization Equation................................................. 158

NIST TDE Watson Heat of Vaporization Equation .................................... 158

Clausius-Clapeyron Equation ............................................................... 159

Molar Volume and Density Models ................................................................. 159

API Liquid Volume ............................................................................. 160

Brelvi-O'Connell ................................................................................ 161

Clarke Aqueous Electrolyte Volume ...................................................... 161

COSTALD Liquid Volume..................................................................... 164

Debye-Hückel Volume ........................................................................ 165

Liquid Constant Molar Volume Model .................................................... 166

Rackett/DIPPR/PPDS/IK-CAPE Liquid Molar Volume ................................ 167

Rackett/Campbell-Thodos Mixture Liquid Volume ................................... 171

Modified Rackett Liquid Molar Volume................................................... 173

Aspen/DIPPR/IK-CAPE Solid Molar Volume ............................................ 174

Liquid Volume Quadratic Mixing Rule.................................................... 175

Heat Capacity Models ..................................................................................176

Aqueous Infinite Dilution Heat Capacity ................................................ 176

Criss-Cobble Aqueous Infinite Dilution Ionic Heat Capacity ...................... 177

DIPPR/PPDS/IK-CAPE Liquid Heat Capacity ........................................... 177

2 Contents

Aspen/DIPPR/Barin/PPDS/IK-CAPE Ideal Gas Heat Capacity .................... 181

Aspen/DIPPR/Barin/IK-CAPE Solid Heat Capacity ................................... 185

Solubility Correlations .................................................................................. 187

Henry's Constant...............................................................................187

Water Solubility ................................................................................ 188

Hydrocarbon Solubility ....................................................................... 189

Other Thermodynamic Property Models .......................................................... 190

Cavett ............................................................................................. 190

Barin Equations for Gibbs Energy, Enthalpy, Entropy, and Heat Capacity ... 190

Electrolyte NRTL Enthalpy................................................................... 193

Electrolyte NRTL Gibbs Free Energy ..................................................... 194

Liquid Enthalpy from Liquid Heat Capacity Correlation ............................ 196

Enthalpies Based on Different Reference States ..................................... 196

Helgeson Equations of State ............................................................... 201

Quadratic Mixing Rule ........................................................................ 203

Viscosity Models.......................................................................................... 206

Andrade Liquid Mixture Viscosity ......................................................... 206

Andrade/DIPPR/PPDS/IK-CAPE Pure Component Liquid Viscosity .............. 207

API Liquid Viscosity ........................................................................... 211

API 1997 Liquid Viscosity.................................................................... 211

Aspen Liquid Mixture Viscosity............................................................. 212

ASTM Liquid Mixture Viscosity ............................................................. 212

Chapman-Enskog-Brokaw/DIPPR/PPDS/IK-CAPE Vapor Viscosity .............. 213

Chapman-Enskog-Brokaw-Wilke Mixing Rule ......................................... 216

Chung-Lee-Starling Low-Pressure Vapor Viscosity .................................. 218

Chung-Lee-Starling Viscosity .............................................................. 220

Dean-Stiel Pressure Correction ............................................................ 222

IAPS Viscosity for Water..................................................................... 222

Jones-Dole Electrolyte Correction......................................................... 223

Letsou-Stiel ...................................................................................... 225

Lucas Vapor Viscosity ........................................................................ 225

TRAPP Viscosity Model ....................................................................... 227

Twu Liquid Viscosity .......................................................................... 227

Viscosity Quadratic Mixing Rule ........................................................... 229

Thermal Conductivity Models ........................................................................ 229

Chung-Lee-Starling Thermal Conductivity ............................................. 230

IAPS Thermal Conductivity for Water.................................................... 231

Li Mixing Rule ................................................................................... 232

Riedel Electrolyte Correction ............................................................... 232

Sato-Riedel/DIPPR/IK-CAPE Liquid Thermal Conductivity......................... 233

Solid Thermal Conductivity Polynomial ................................................. 236

Stiel-Thodos/DIPPR/PPDS/IK-CAPE Vapor Thermal Conductivity ............... 237

Stiel-Thodos Pressure Correction Model ................................................ 239

Vredeveld Mixing Rule........................................................................ 240

TRAPP Thermal Conductivity Model ...................................................... 240

Wassiljewa-Mason-Saxena Mixing Rule ................................................. 241

Diffusivity Models ........................................................................................242

Chapman-Enskog-Wilke-Lee (Binary) ................................................... 242

Chapman-Enskog-Wilke-Lee (Mixture).................................................. 243

Dawson-Khoury-Kobayashi (Binary) ..................................................... 244

Contents 3

Dawson-Khoury-Kobayashi (Mixture) ...................................................244

Nernst-Hartley .................................................................................. 245

Wilke-Chang (Binary)......................................................................... 246

Wilke-Chang (Mixture) ....................................................................... 247

Surface Tension Models................................................................................ 248

Liquid Mixture Surface Tension ............................................................ 248

API Surface Tension........................................................................... 249

IAPS Surface Tension for Water........................................................... 249

Hakim-Steinberg-Stiel/DIPPR/PPDS/IK-CAPE Liquid Surface Tension......... 249

Onsager-Samaras ............................................................................. 253

Modified MacLeod-Sugden .................................................................. 254

General Enthalpy and Density Models............................................................. 255

General Density Polynomial ................................................................ 256

General Heat Capacity Polynomial........................................................ 256

Enthalpy and Density Models for Coal and Char ............................................... 257

General Coal Enthalpy Model............................................................... 260

IGT Coal Density Model ...................................................................... 266

IGT Char Density Model...................................................................... 266

Option Codes for Transport Property Models.................................................... 268

Option Codes for Activity Coefficient Models .................................................... 269

Option Codes for Equation of State Models...................................................... 271

Soave-Redlich-Kwong Option Codes............................................................... 274

Option Codes for K-Value Models................................................................... 276

Option Codes for Enthalpy Models.................................................................. 276

Option Codes for Gibbs Energy Models ........................................................... 278

Option Codes for Liquid Volume Models .......................................................... 279

Index ..................................................................................................................280

4 Contents

1 Introduction

This manual describes the property models available in the Aspen Physical

Property System and defines the parameters used in each model. The

description for each model lists the parameter names used to enter values on

the Properties Parameters forms.

This manual also lists the pure component temperature-dependent properties

that the Aspen Physical Property System can calculate from a model that

supports several equations or submodels. See Pure Component Temperature-

Dependent Properties (below).

Many parameters have default values indicated in the Default column. A dash

(–) indicates that the parameter has no default value and you must provide a

value. If a parameter is missing, calculations stop. The lower limit and upper

limit for each parameter, when available, indicate the reasonable bounds for

the parameter. The limits are used to detect grossly erroneous parameter

values.

The property models are divided into the following categories:

• Thermodynamic property models

• Transport property models

• Nonconventional solid property models

The property types for each category are discussed in separate sections. The

following table (below) provides an organizational overview of this manual.

The tables labeled Thermodynamic Property Models, Transport Property

Models, and Nonconventional Solid Property Models present detailed lists of

models. These tables also list the Aspen Physical Property System model

names, and their possible use in different phase types, for pure components

and mixtures.

Electrolyte and conventional solid property models are presented in

Thermodynamic Property Models.

1 Introduction 5

Categories of Models

Category Sections

Thermodynamic Equation-of-State Models

Property Models Activity Coefficient Models (Including Electrolyte Models)

Vapor Pressure and Liquid Fugacity Models

Heat of Vaporization Models

Molar Volume and Density Models

Heat Capacity Models

Solubility Correlations

Other

Transport Property Viscosity Models

Models Thermal Conductivity Models

Diffusivity Models

Surface Tension Models

Nonconventional Solid General Enthalpy and Density Models

Property Models Enthalpy and Density Models for Coal and Char

Dependent Parameters

Some temperature-dependent parameters may be based on expressions

which involve logarithmic or reciprocal temperature terms. When the

coefficient of any such term is non-zero, in many cases the entire expression

must be calculated assuming that all the coefficients are in absolute

temperature units. In other cases, terms are independent from one another,

and only certain terms may require calculation using absolute temperature

units. Notes in the models containing such terms explain exactly which

coefficients are affected by this treatment.

When absolute temperature units are forced in this way, this affects the units

for coefficients you have entered as input parameters. If your input

temperature units are Fahrenheit (F), then Rankine (R) is used instead. If

your input units are Celsius (C), then Kelvin (K) is used instead.

If only constant and positive powers of temperature are present in the

expression, then your specified input units are used.

If the parameters include temperature limits, the limits are always interpreted

in user input units even if the expression is forced to absolute units.

Some equations may include a dimensionless parameter, the reduced

temperature Tr = T / Tc. This reduced temperature is calculated using

absolute temperature units. In most cases, input parameters associated with

such equations do not have temperature units.

6 1 Introduction

Pure Component Temperature-

Dependent Properties

The following table lists the pure component temperature-dependent

properties that the Aspen Physical Property System can calculate from a

model that supports several equations or submodels.

For example, the Aspen Physical Property System can calculate heat of

vaporization using these equations:

• Watson

• DIPPR

• PPDS

• IK-CAPE

Submodel-Selection Default DIPPR

Parameter Element Equation

Property Number Available Submodels Number

Solid Volume THRSWT/1 Aspen, DIPPR, IK-CAPE 100

Liquid Volume THRSWT/2 Aspen, DIPPR, PPDS, 105/116†

IK-CAPE

Liquid Vapor Pressure THRSWT/3 Aspen, Wagner, 101/115†

BARIN, PPDS, IK-CAPE

Heat of Vaporization THRSWT/4 Aspen, DIPPR, PPDS, 106

IK-CAPE

Solid Heat Capacity THRSWT/5 Aspen, DIPPR, BARIN, 100

IK-CAPE

Liquid Heat Capacity THRSWT/6 DIPPR, PPDS, BARIN, 100/114†

IK-CAPE

Ideal Gas Heat THRSWT/7 Aspen, DIPPR, BARIN, 107

Capacity PPDS, IK-CAPE

Second Virial THRSWT/8 DIPPR 104

Coefficient

Liquid Viscosity TRNSWT/1 Aspen, DIPPR, PPDS, 101

IK-CAPE

Vapor Viscosity TRNSWT/2 Aspen, DIPPR, PPDS, 102

IK-CAPE

Liquid Thermal TRNSWT/3 Aspen, DIPPR, PPDS, 100

Conductivity IK-CAPE

Vapor Thermal TRNSWT/4 Aspen, DIPPR, PPDS, 102

Conductivity IK-CAPE

Liquid Surface TRNSWT/5 Aspen, DIPPR, PPDS, 106

Tension IK-CAPE

†

Equations 114 through 116 are used as the default only for water.

Which equation is actually used to calculate the property for a given

component depends on which parameters are available. If parameters are

available for more than one equation, the Aspen Physical Property System

uses the parameters that were entered or retrieved first from the databanks.

1 Introduction 7

The selection of submodels is driven by the data hierarchy, and controlled by

the submodel-selection parameters.

The thermodynamic properties use the THRSWT (thermo switch) submodel-

selection parameter, and the transport properties use the TRNSWT (transport

switch) submodel-selection parameter.

As the previous table shows, a property is associated with an element of the

submodel-selection parameter. For example, THRSWT element 1 controls the

submodel for solid volume.

The following table shows the values for THRSWT or TRNSWT, and the

corresponding submodels.

Parameter Values

(Equation Number) Submodel

0 Aspen

1 to 116 DIPPR

200 BARIN

301 to 302 PPDS or property-specific methods

400 PML

401 to 404 IK-CAPE

501 to 515 NIST

TRNSWT) that are set to use the correct equations that are consistent with

the available parameters. For example, suppose that parameters for the

DIPPR equation 106 are available for liquid surface tension. For that

component, TRNSWT element 5 is set to 106 in the databank. If you are

retrieving data from an in-house or user databank, you should store the

appropriate values for THRSWT and TRNSWT in the databank, using the

appropriate equation number. Otherwise, the Aspen Physical Property System

will search for the parameters needed for the Aspen form of the equations.

If a component is available in more than one databank, the Aspen Physical

Property System uses the data and equations based on the databank list

order on the Components Specifications Selection sheet. For example,

suppose the databank search order is ASPENPCD, then PURE10, and that the

Aspen Physical Property System cannot find the parameters for a particular

submodel (equation) in the ASPENPCD databank. If the PURE10 databank

contains parameters for another equation, the Aspen Physical Property

System will use that equation (most likely the DIPPR equation) to calculate

the property for that component.

If your calculation contains any temperature-dependent property parameters,

(such as CPIGDP for DIPPR ideal gas heat capacity, entered on the Properties

Parameters Pure Component form), the Aspen Physical Property System sets

the corresponding THRSWT and TRNSWT elements for that component to the

default values shown in the table above. This default setting might not always

be correct. If you know the equation number, you should enter it directly on

the Properties Parameters Pure-Components form. For example, suppose you

want to use the:

• DIPPR equation form of heat of vaporization (DHVLDP) for a component

• Aspen equations for the remaining temperature dependent properties

8 1 Introduction

Set the fourth element of the THRSWT parameter to 106, and the 1-3 and 5-8

elements to 0. If you want to set the other temperature-dependent properties

to use what is defined for that component in the databank, leave the element

blank.

The following table lists the available DIPPR equations and the corresponding

equation (submodel) number.

Equation

Number Equation Form

100

101

102

103

104

105

106

107

114

116

temperature units.

This chapter describes the Aspen, DIPPR, BARIN, IK-CAPE, and PPDS

equations for each property. For descriptions of the the BARIN equations for

heat capacity and enthalpy, see BARIN Equations for Gibbs Energy, Enthalpy,

Entropy, and Heat Capacity.

Extrapolation Methods

Many temperature dependent property models have upper and lower

temperature limits. The Aspen Physical Property System usually extrapolates

linearly beyond such limits. It calculates the slope of the property-versus-

temperature curve, or the ln(property)-versus-temperature curve for models

expressed in logarithmic form, at the upper or lower temperature limit. For

temperatures beyond the limit, it uses a linear model with this slope which

meets the curve from the equation at the temperature limit. Thus the model

is:

1 Introduction 9

For T beyond the upper or lower limit, where Tlim is that limit and Z is the

property or ln(property) as appropriate. Some liquid molar volume models are

actually molar density models which then return the reciprocal of the density

as the liquid molar volume. In these models, the extrapolation occurs for the

density calculation.

There are certain exceptions, detailed below.

Temperature

This applies to property models expressed in the form (where a(T) includes

any additional dependency on temperature):

For these models, the extrapolation maintains the slope of ln(property) versus

1/T. This applies to the Extended Antoine vapor pressure equation and the

Andrade and DIPPR liquid viscosity equations. Note that the equation for

Henry's Constant is extrapolated by ln(Henry) versus T.

The Aspen Ideal Gas Heat Capacity model has an explicit equation for

extrapolation at temperatures below the lower limit, which is described in the

model. At high temperatures it follows the usual rule of extrapolating

property-versus-temperature linearly.

Exception 3: No Extrapolation

The equations for certain models are used directly at all temperatures, so that

no extrapolation is performed. These models are the Wagner vapor pressure

equation, the Aly and Lee equation for the DIPPR Ideal Gas Heat Capacity

(using the CPIGDP parameter), and the Water Solubility and Hydrocarbon

Solubility models. The equations for temperature-dependent binary

interaction parameters are also used directly at all temperatures with no

extrapolation.

10 1 Introduction

2 Thermodynamic Property

Models

Aspen Physical Property System. The following table provides a list of

available models, with corresponding Aspen Physical Property System model

names. The table provides phase types for which the model can be used and

information on use of the model for pure components and mixtures.

Aspen Physical Property System thermodynamic property models include

classical thermodynamic property models, such as activity coefficient models

and equations of state, as well as solids and electrolyte models. The models

are grouped according to the type of property they describe.

Phases: V = Vapor; L = Liquid; S = Solid. An X indicates applicable to Pure or

Mixture.

Equation-of-State Models

Property Model Model Name(s) Phase(s) Pure Mixture

ASME Steam Tables ESH2O0,ESH2O VL X —

BWR-Lee-Starling ESBWR0, ESCSTBWR V L X X

Benedict-Webb-Rubin-Starling ESBWRS, ESBWRS0 VL X X

Hayden-O'Connell ESHOC0,ESHOC V X X

HF equation-of-state ESHF0, ESHF V X X

Ideal Gas ESIG0, ESIG V X X

Lee-Kesler ESLK VL — X

Lee-Kesler-Plöcker ESLKP0,ESLKP VL X X

NBS/NRC Steam Tables ESSTEAM0,ESSTEAM VL X —

Nothnagel ESNTH0,ESNTH V X X

PC-SAFT ESPSAFT, ESPSAFT0 VL X X

Peng-Robinson ESPR0, ESPR VL X X

Standard Peng-Robinson ESPRSTD0,ESPRSTD VL X X

Peng-Robinson-Wong-Sandler ESPRWS0,ESPRWS VL X X

Peng-Robinson-MHV2 ESPRV20,ESPRV2 VL X X

Property Model Model Name(s) Phase(s) Pure Mixture

Predictive SRK ESRKSV10, ESRKSV1 V L X X

Redlich-Kwong ESRK0, ESRK V X X

Redlich-Kwong-Aspen ESRKA0,ESRKA VL X X

Redlich-Kwong-Soave ESRKSTD0,ESRKSTD VL X X

Redlich-Kwong-Soave-Boston- ESRKS0, ESRKS VL X X

Mathias

Redlich-Kwong-Soave-Wong- ESRKSWS0, ESRKSWS V L X X

Sandler

Redlich-Kwong-Soave-MHV2 ESRKSV20, ESRKSV2 V L X X

Schwartzentruber-Renon ESRKU0,ESRKU VL X X

Soave-Redlich-Kwong ESSRK0, ESSRK VL X X

SRK-Kabadi-Danner ESSRK0, ESSRK VL X X

SRK-ML ESRKSML0, ESRKSML V L X X

VPA/IK-CAPE equation-of-state ESVPA0, ESVPA V X X

Peng-Robinson Alpha functions — VL X —

RK-Soave Alpha functions — VL X —

Huron-Vidal mixing rules — VL — X

MHV2 mixing rules — VL — X

PSRK mixing rules — VL — X

Wong-Sandler mixing rules — VL — X

Property Model Model Name Phase(s) Pure Mixture

Bromley-Pitzer GMPT2 L — X

Chien-Null GMCHNULL L — X

Constant Activity Coefficient GMCONS S — X

COSMO-SAC COSMOSAC L — X

Electrolyte NRTL GMELC L L1 L2 — X

ENRTL-SAC ENRTLSAC L — X

Hansen HANSEN L — X

Ideal Liquid GMIDL L — X

NRTL(Non-Random-Two-Liquid) GMRENON L L1 L2 — X

NRTL-SAC NRTLSAC L — X

Pitzer GMPT1 L — X

Polynomial Activity Coefficient GMPOLY LS — X

Redlich-Kister GMREDKIS LS — X

Scatchard-Hildebrand GMXSH L — X

Three-Suffix Margules GMMARGUL LS — X

UNIFAC GMUFAC L L1 L2 — X

UNIFAC (Lyngby modified) GMUFLBY L L1 L2 — X

UNIFAC (Dortmund modified) GMUFDMD L L1 L2 — X

UNIQUAC GMUQUAC L L1 L2 — X

van Laar GMVLAAR L — X

Property Model Model Name Phase(s) Pure Mixture

Wagner interaction parameter GMWIP S — X

Wilson GMWILSON L — X

Wilson model with liquid molar GMWSNVOL L — X

volume

Property Model Model Name Phase(s) Pure Mixture

Extended Antoine/Wagner PL0XANT L L1 L2 X —

API Sour SWEQ L — X

Braun K-10 BK10 L — X

Chao-Seader PHL0CS L X —

Grayson-Streed PHL0GS L X —

Kent-Eisenberg ESAMINE L — X

Maxwell-Bonnell PL0MXBN L L1 L2 X —

Solid Antoine PS0ANT S X —

Property Model Model Name Phase(s) Pure Mixture

DIPPR/Watson/PPDS/IK-CAPE DHVLWTSN L X —

Clausius-Clapeyron Equation DHVLWTSN L X —

Property Model Model Name Phase(s) Pure Mixture

API Liquid Volume VL2API L — X

Brelvi-O'Connell VL1BROC L — X

Clarke Aqueous Electrolyte VAQCLK L — X

Volume

COSTALD Liquid Volume VL0CTD,VL2CTD L X X

Debye-Hückel Volume VAQDH L — X

Liquid Constant Molar Volume VL0CONS L X —

Rackett / DIPPR/ PPDS / IK- VL0RKT,VL2RKT L X —

CAPE Liquid Volume

Rackett/Campbell-Thodos VL2RKT L X X

Mixture Liquid Volume

Modified Rackett VL2MRK L X X

Aspen/DIPPR/IK-CAPE Solid VS0POLY S X —

Molar Volume

Liquid Volume Quadratic Mixing VL2QUAD L — X

Rule

Property Model Model Name Phase(s) Pure Mixture

Aqueous Infinite Dilution Heat — L — X

Capacity Polynomial

Property Model Model Name Phase(s) Pure Mixture

Criss-Cobble Aqueous Infinite — L — X

Dilution Ionic Heat Capacity

DIPPR / PPDS / IK-CAPE Liquid HL0DIP L X —

Heat Capacity

Aspen / DIPPR / Barin / PPDS / — V X X

IK-CAPE Ideal Gas Heat

Capacity

Aspen / DIPPR / Barin / IK-CAPE HS0POLY S X —

Solids Heat Capacity

Property Model Model Name Phase(s) Pure Mixture

Henry's constant HENRY1 L — X

Water solubility — L — X

Hydrocarbon solubility — L — X

Other Models

Property Model Model Name Phase(s) Pure Mixture

Cavett Liquid Enthalpy DHL0CVT, DHL2CVT L X X

Departure

BARIN Equations for Gibbs — SLV X —

Energy, Enthalpy, Entropy and

Heat Capacity

Electrolyte NRTL Enthalpy HAQELC, HMXELC L — X

Electrolyte NRTL Gibbs Energy GAQELC, GMXELC L — X

Liquid Enthalpy from Liquid Heat DHL0DIP L X X

Capacity Correlation

Enthalpies Based on Different DHL0HREF LV X X

Reference States

Helgeson Equations of State — L — X

Quadratic Mixing Rule — LV — X

Equation-of-State Models

The Aspen Physical Property System has the following built-in equation-of-

state property models. This section describes the equation-of-state property

models available.

Model Type

ASME Steam Tables Fundamental

BWR-Lee-Starling Virial

Benedict-Webb-Rubin-Starling Virial

Hayden-O'Connell Virial and association

HF Equation-of-State Ideal and association

Huron-Vidal mixing rules Mixing rules

Ideal Gas Ideal

Model Type

Lee-Kesler Virial

Lee-Kesler-Plöcker Virial

MHV2 mixing rules Mixing rules

NBS/NRC Steam Tables Fundamental

Nothnagel Ideal

PC-SAFT Association

Peng-Robinson Cubic

Standard Peng-Robinson Cubic

Peng-Robinson Alpha functions Alpha functions

Peng-Robinson-MHV2 Cubic

Peng-Robinson-Wong-Sandler Cubic

Predictive SRK Cubic

PSRK mixing rules Mixing rules

Redlich-Kwong Cubic

Redlich-Kwong-Aspen Cubic

Standard Redlich-Kwong-Soave Cubic

Redlich-Kwong-Soave-Boston-Mathias Cubic

Redlich-Kwong-Soave-MHV2 Cubic

Redlich-Kwong-Soave-Wong-Sandler Cubic

RK-Soave Alpha functions Alpha functions

Schwartzentruber-Renon Cubic

Soave-Redlich-Kwong Cubic

SRK-Kabadi-Danner Cubic

SRK-ML Cubic

VPA/IK-CAPE equation-of-state Ideal and association

Wong-Sandler mixing rules Mixing rules

The ASME steam tables are implemented like any other equation-of-state in

the Aspen Physical Property System. The steam tables can calculate any

thermodynamic property of water or steam and form the basis of the STEAM-

TA property method. There are no parameter requirements. The ASME steam

tables are less accurate than the NBS/NRC steam tables.

References

ASME Steam Tables, Thermodynamic and Transport Properties of Steam,

(1967).

K. V. Moore, Aerojet Nuclear Company, prepared for the U.S. Atomic Energy

Commision, ASTEM - A Collection of FORTRAN Subroutines to Evaluate the

1967 ASME equations of state for water/steam and derivatives of these

equations.

BWR-Lee-Starling

The Benedict-Webb-Rubin-Lee-Starling equation-of-state is the basis of the

BWR-LS property method. It is a generalization by Lee and Starling of the

virial equation-of-state for pure fluids by Benedict, Webb and Rubin. The

equation is used for non-polar components, and can manage hydrogen-

containing systems.

General Form:

Where:

Mixing Rules:

Where:

Name/Element Limit Limit

TCBWR Tci TC X 5.0 2000.0 TEMPERATURE

VCBWR Vci* VC X 0.001 3.5 MOLE-

VOLUME

BWRGMA γi OMEGA X -0.5 3.0 —

Binary interaction parameters BWRKV and BWRKT are available in the Aspen

Physical Property System for a large number of components. (See Physical

Property Data, Chapter 1).

References

M.R. Brulé, C.T. Lin, L.L. Lee, and K.E. Starling, AIChE J., Vol. 28, (1982) p.

616.

Brulé et al., Chem. Eng., (Nov., 1979) p. 155.

Watanasiri et al., AIChE J., Vol. 28, (1982) p. 626.

Benedict-Webb-Rubin-Starling

The Benedict-Webb-Rubin-Starling equation-of-state is the basis of the BWRS

property method. It is a modification by Han and Starling of the virial

equation-of-state for pure fluids by Benedict, Webb and Rubin. This equation-

of-state can be used for hydrocarbon systems that include the common light

gases, such as H2S, CO2 and N2.

The form of the equation-of-state is:

Where:

kij = kji

In the mixing rules given above, A0i, B0i, C0i, D0i, E0i, ai, bi, ci, di, αi, γi are pure

component constants which can be input by the user. If the values of these

parameters are not given, the Aspen Physical Property System will calculate

them using the critical temperature, the critical volume (or critical density),

the acentric factor and generalized correlations given by Han and Starling.

When water is present, by default Benedict-Webb-Rubin-Starling uses the

steam table to calculate the enthalpy, entropy, Gibbs energy, and molar

volume of water. The total properties are mole-fraction averages of these

values with the properties calculated by the equation of state for other

components. Fugacity coefficient is not affected. An option code can disable

this use of the steam table.

For best results, the binary parameter kij must be regressed using phase-

equilibrium data such as VLE data.

Parameter SymbolDefault MDS Lower Upper Units

Name/ Limit Limit

Element

BWRSTC Tci TC x 5.0 2000.0 TEMPERATURE

BWRSVC Vci VC x 0.001 3.5 MOLE-VOLUME

BWRSOM ωi OMEGA x –0.5 2.0 –

BWRSA/1 B0i fcn(ωi ,Vci , Tci) x – – MOLE-VOLUME

BWRSA/2 A0i fcn(ωi ,Vci , Tci) x – – PRESSURE * MOLE-

VOL^2

BWRSA/3 C0i fcn(ωi ,Vci , Tci) x – – PRESSURE *

TEMPERATURE^2 *

MOLE-VOLUME^2

BWRSA/4 γi fcn(ωi ,Vci , Tci) x – – MOLE-VOLUME^2

BWRSA/6 ai fcn(ωi ,Vci , Tci) x – – PRESSURE * MOLE-

VOL^3

BWRSA/7 αi fcn(ωi ,Vci , Tci) x – – MOLE-VOLUME^3

BWRSA/8 ci fcn(ωi ,Vci , Tci) x – – PRESSURE *

TEMPERATURE^2 *

MOLE-VOLUME^3

BWRSA/9 D0i fcn(ωi ,Vci , Tci) x – – PRESSURE *

TEMPERATURE^3 *

MOLE-VOLUME^2

BWRSA/10 di fcn(ωi ,Vci , Tci) x – – PRESSURE *

TEMPERATURE * MOLE-

VOLUME^3

Parameter SymbolDefault MDS Lower Upper Units

Name/ Limit Limit

Element

BWRSA/11 E0i fcn(ωi ,Vci , Tci) x – – PRESSURE *

TEMPERATURE^4 *

MOLE-VOLUME^2

BWRAIJ kij – x – – –

Parameter Methane Ethane Propane n-Butane

B0i 0.723251 0.826059 0.964762 1.56588

A0i 7520.29 13439.30 18634.70 32544.70

8 9 9

C0i 2.71092x10 2.95195x10 7.96178x10 1.37436x1010

10 11 11

D0i 1.07737x10 2.57477x10 4.53708x10 3.33159x1011

E0i 3.01122x1010 1.46819x1013 2.56053x1013 2.30902x1012

bi 0.925404 3.112060 5.462480 9.140660

ai 2574.89 22404.50 40066.40 71181.80

7

di 47489.1 702189.0 1.50520x10 3.64238x107

αi 0.468828 0.909681 2.014020 4.009850

ci 4.37222x108 6.81826x109 2.74461x1010 7.00044x1010

γi 1.48640 2.99656 4.56182 7.54122

B0i 2.44417 2.66233 3.60493 4.86965

A0i 51108.20 45333.10 77826.90 81690.60

10 10 10

C0i 2.23931x10 5.26067x10 6.15662x10 9.96546x1010

12 12 12

D0i 1.01769x10 5.52158x10 7.77123x10 7.90575x1012

E0i 3.90860x1013 6.26433x1014 6.36251x1012 3.46419x1013

bi 16.607000 29.498300 27.441500 10.590700

ai 162185.00 434517.00 359087.00 131646.00

7 7

di 3.88521x10 3.27460x10 8351150.0 1.85906x108

αi 7.067020 9.702300 21.878200 34.512400

ci 1.35286x1011 3.18412x1011 3.74876x1011 6.42053x1011

γi 11.85930 14.87200 24.76040 21.98880

References

M. Benedict, G. B. Webb, and L. C. Rubin, J. Chem. Phys., Vol. 8, (1940), p.

334.

M. S. Han, and K. E. Starling , "Thermo Data Refined for LPG. Part 14:

Mixtures", Hydrocarbon Processing, Vol. 51, No. 5, (1972), p.129.

K. E. Starling, "Fluid Themodynamic Properties for Light Petroleum Systems",

Gulf Publishing Co., Houston, Texas (1973).

Hayden-O'Connell

The Hayden-O'Connell equation-of-state calculates thermodynamic properties

for the vapor phase. It is used in property methods NRTL-HOC, UNIF-HOC,

UNIQ-HOC, VANL-HOC, and WILS-HOC, and is recommended for nonpolar,

polar, and associating compounds. Hayden-O'Connell incorporates the

chemical theory of dimerization. This model accounts for strong association

and solvation effects, including those found in systems containing organic

acids, such as acetic acid. The equation-of-state is:

Where:

, with

, where

, with

, where

, and

Cross-Interactions

The previous equations are valid for dimerization and cross-dimerization if

these mixing rules are applied:

η = 0 unless a special solvation contribution can be justified (for example, i

and j are in the same class of compounds). Many η values are present in the

Aspen Physical Property System.

Chemical Theory

the entire mixture is treated according to the chemical theory of dimerization.

The chemical reaction for the general case of a mixture of dimerizing

components i and j is:

The equation-of-state becomes:

with

In this case, molar volume is equal to V/nt.

This represents true total volume over the true number of species nt.

However, the reported molar volume is V/na.

This represents the true total volume over the apparent number of species na.

If dimerization does not occur, na is defined as the number of species. V/na

reflects the apparently lower molar volume of an associating gas mixture.

The chemical equilibrium constant for the dimerization reaction on pressure

basis Kp, is related to the true mole fractions and fugacity coefficients:

Where:

yi and yj = True mole fractions of monomers

yij = True mole fraction of dimer

ϕi = True fugacity coefficient of component i

Kij = Equilibrium constant for the dimerization of i and j, on a

pressure basis

=

= 0 for

Apparent mole fractions yia are reported, but in the calculation real mole

fractions yi, yj, and yij are used.

The heat of reaction due to each dimerization is calculated according to:

The sum of the contributions of all dimerization reactions, corrected for the

ratio of apparent and true number of moles is added to the molar enthalpy

departure .

Parameter Name/ Symbol Default MDS Lower Upper Units

Element Limit Limit

TC Tci — — 5.0 2000.0 TEMPERATURE

PC pci — — 105 108 PRESSURE

RGYR rigyr — — 10 -11

5x10 -9

LENGTH

-24

MUP pi — — 0.0 5x10 DIPOLEMOMENT

HOCETA η 0.0 X — — —

The binary parameters HOCETA for many component pairs are available in the

Aspen Physical Property System. These parameters are retrieved

automatically when you specify any of the following property methods: NRTL-

HOC, UNIF-HOC, UNIQ-HOC, VANL-HOC, and WILS-HOC.

References

J.G. Hayden and J.P. O'Connell, "A Generalized Method for Predicting Second

Virial Coefficients," Ind. Eng. Chem., Process Des. Dev., Vol. 14,No. 3,

(1974), pp. 209 – 216.

HF Equation-of-State

HF forms oligomers in the vapor phase. The non-ideality in the vapor phase is

found in important deviations from ideality in all thermodynamic properties.

The HF equation accounts for the vapor phase nonidealities. The model is

based on chemical theory and assumes the formation of hexamers.

Species like HF that associate linearly behave as single species. For example,

they have a vapor pressure curve, like pure components. The component on

which a hypothetical unreacted system is based is often called the apparent

(or parent) component. Apparent components react to the true species.

Electrolyte Calculation in Physical Property Methods discusses apparent and

true species. Abbott and van Ness (1992) provide details and basic

thermodynamics of reactive systems.

The temperature-dependent hexamerization equilibrium constant, can fit the

experimentally determined association factors. The built-in functionality is:

(1)

The constants C0 and C1 are from Long et al. (1943), and C2 and C3 are set to

0. The correlation is valid between 270 and 330 K, and can be extrapolated to

about 370 K (cf. sec. 4). Different sets of constants can be determined by

experimental data regression.

The non-ideality of HF is often expressed using the association factor, f,

indicating the ratio of apparent number of species to the real number or

species. Assuming the ideal gas law for all true species in terms of (p, V, T)

behavior implies:

(2)

Where the true number of species is given by 1/f. The association factor is

easily determined from (p, V, T) experiments. For a critical evaluation of data

refer to Vanderzee and Rodenburg (1970).

If only one reaction is assumed for a mixture of HF and its associated species,

(refer to Long et al., 1943), then:

(3)

represents the true partial pressure of the hexamer, then the equilibrium

constant is defined as:

(4)

p = p1 + p6 (5)

If all hexamer were dissociated, the apparent total pressure would be the

hypothetical pressure where:

pa = p1 + 6p6 = p + 5p6 (6)

When physical ideality is assumed, partial pressures and mole fractions are

proportional. The total pressure in equation 5 represents the true number of

species. The apparent total pressure from equation 6 represents the apparent

number of species:

(7)

Note that the outcome of equation 7 is independent of the assumption of

ideality. Equation 7 can be used to compute the number of true species 1/f

for a mixture containing HF, but the association factor is defined differently.

If p1 and p6 are known, the molar volume or density of a vapor containing HF

can be calculated using equations 2 and 7. The molar volume calculated is the

true molar volume for 1 apparent mole of HF. This is because the volume of 1

mole of ideal gas (the true molar volume per true number of moles) is always

equal to about 0.0224 m3/mol at 298.15 K.

If you assume the ideal gas law for a mixture containing HF, the apparent HF

mole fraction is:

(8)

apparent partial pressure of HF) is the hypothetical partial pressure only if all

of the hexamer was dissociated. If you substitute equation 4, then equation 8

becomes:

(9)

K is known from Long et al., or can be regressed from (p,V,T) data. The

apparent mole fraction of HF, ya, is known to the user and the simulator, but

p1, or y = p1/p must also be known in order to calculate the thermodynamic

properties of the mixture. Equation 9 must be solved for p1.

Equation 9 can be written as a polynomial in p1 of degree 6:

K(6 - 5ya)(p1)6 + p1 - pya = 0 (9a)

A second order Newton-Raphson technique is used to determine p1. Then p6

can be calculated by equation 5, and f is known (equation 7).

The apparent fugacity coefficient is related to the true fugacity coefficient and

mole fractions:

(10)

The ratio of the true number of species to the apparent number of species is

similar to the correction applied in equation 2. Since the ideal gas law is

assumed, the apparent fugacity coefficient is given by the equation. All

variables on the right side are known.

(11)

For pure HF, ya = 1:

From the fugacity coefficient, the Gibbs energy departure of the mixture or

pure apparent components can be calculated:

(12)

(12a)

For the enthalpy departure, the heat of reaction is considered. For an

arbitrary gas phase reaction:

(13)

(14)

energy of a component. Equation 4 represents the first two terms of the

general equation 14. The second or third equality relates the equilibrium

constant to the Gibbs energy of reaction, which is thus related to the enthalpy

of reaction:

(15)

the heat of reaction, per apparent number of moles:

(16)

(17)

From the Gibbs energy departure and enthalpy departure, the entropy

departure can be calculated:

(18)

by straightforward differentiation.

Usage

The HF equation-of-state should only be used for vapor phase calculations. It

is not suited for liquid phase calculations.

The HF equation-of-state can be used with any activity coefficient model for

nonelectrolyte VLE. Using the Electrolyte NRTL model and the data package

MHF2 is strongly recommended for aqueous mixtures (de Leeuw and

Watanasiri, 1993).

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

ESHFK/1 C0 43.65 — — — —

ESHFK/2 C1 -8910 — — — —

ESHFK/3 C2 0 — — — —

ESHFK/4 C3 0 — — — —

References

M. M. Abbott and H. C. van Ness, "Thermodynamics of Solutions Containing

Reactive Species, a Guide to Fundamentals and Applications," Fluid Phase Eq.,

Vol. 77, (1992) pp. 53 – 119.

V. V. De Leeuw and S. Watanasiri, "Modelling Phase Equilibria and Enthalpies

of the System Water and Hydroflouric Acid Using an HF Equation-of-state in

Conjunction with the Electrolyte NRTL Activity Coefficient Model," Paper

presented at the 13th European Seminar on Applied Thermodynamics, June 9

– 12, Carry-le-Rouet, France, 1993.

R. W. Long, J. H. Hildebrand, and W. E. Morrell, "The Polymerization of

Gaseous Hydrogen and Deuterium Flourides," J. Am. Chem. Soc., Vol. 65,

(1943), pp. 182 – 187.

C. E. Vanderzee and W. WM. Rodenburg, "Gas Imperfections and

Thermodynamic Excess Properties of Gaseous Hydrogen Fluoride," J. Chem.

Thermodynamics, Vol. 2, (1970), pp. 461 – 478.

Ideal Gas

The ideal gas law (ideal gas equation-of-state) combines the laws of Boyle

and Gay-Lussac. It models a vapor as if it consisted of point masses without

any interactions. The ideal gas law is used as a reference state for equation-

of-state calculations, and can be used to model gas mixtures at low pressures

(without specific gas phase interactions).

The equation is:

p = RT / Vm

Lee-Kesler

This equation-of-state model is based on the work of Lee and Kesler (1975).

In this equation, the volumetric and thermodynamic properties of fluids based

on the Curl and Pitzer approach (1958) have been analytically represented by

a modified Benedict-Webb-Rubin equation-of-state (1940). The model

calculates the molar volume, enthalpy departure, Gibbs free energy

departure, and entropy departure of a mixture at a given temperature,

pressure, and composition for either a vapor or a liquid phase. Partial

derivatives of these quantities with respect to temperature can also be

calculated.

Unlike the other equation-of-state models, this model does not calculate

fugacity coefficients.

The compressibility factor and other derived thermodynamic functions of

nonpolar and slightly polar fluids can be adequately represented, at constant

reduced temperature and pressure, by a linear function of the acentric factor.

In particular, the compressibility factor of a fluid whose acentric factor is ω, is

given by the following equation:

Z = Z(0) + ωZ(1)

Where:

Z(0) = Compressibility factor of a simple fluid (ω = 0)

Z(1) = Deviation of the compressibility factor of the real fluid from Z(0)

Z(0) and Z(1) are assumed universal functions of the reduced temperature and

pressure.

Curl and Pitzer (1958) were quite successful in correlating thermodynamic

and volumetric properties using the above approach. Their application

employed tables of properties in terms of reduced temperature and pressure.

A significant weakness of this method is that the various properties (for

example, entropy departure and enthalpy departure) will not be exactly

thermodynamically consistent with each other. Lee and Kesler (1975)

overcame this drawback by an analytic representation of the tables with an

equation-of-state. In addition, the range was extended by including new data.

In the Lee-Kesler implementation, the compressibility factor of any fluid has

been written in terms of a simple fluid and a reference as follows:

In the above equation both Z(0) and Z(1) are represented as generalized

equations of the BWR form in terms of reduced temperature and pressure.

Thus,

Equations for the enthalpy departure, Gibbs free energy departure, and

entropy departure are obtained from the compressibility factor using standard

thermodynamic relationships, thus ensuring thermodynamic consistency.

In the case of mixtures, mixing rules (without any binary parameters) are

used to obtain the mixture values of the critical temperature and pressure,

and the acentric factor.

This equation has been found to provide a good description of the volumetric

and thermodynamic properties of mixtures containing nonpolar and slightly

polar components.

Symbol Parameter Name Default Definition

Tc TCLK TC Critical temperature

Pc PCLK PC Critical pressure

Symbol Parameter Name Default Definition

ω OMGLK OMEGA Acentric factor

References

M. Benedict, G. B. Webb, and L. C. Rubin, J. Chem. Phys., Vol. 8, (1940), p.

334.

R. F. Curl and K.S. Pitzer, Ind. Eng. Chem., Vol. 50, (1958), p. 265.

B. I. Lee and M.G. Kesler, AIChE J., Vol. 21, (1975), p. 510.

Lee-Kesler-Plöcker

The Lee-Kesler-Plöcker equation-of-state is the basis for the LK-PLOCK

property method. This equation-of-state applies to hydrocarbon systems that

include the common light gases, such as H2S and CO2. It can be used in gas-

processing, refinery, and petrochemical applications.

The general form of the equation is:

Where:

The fo and fR parameters are functions of the BWR form. The fo parameter is

for a simple fluid, and fR is for reference fluid n-octane.

Vcm =

ω =

Zm =

Where:

Vcij =

Tcij =

Zci =

kij = kji

The binary parameter kij is determined from phase-equilibrium data

regression, such as VLE data. The Aspen Physical Property System stores the

binary parameters for a large number of component pairs. These binary

parameters are used automatically with the LK-PLOCK property method. If

binary parameters for certain component pairs are not available, they can be

estimated using built-in correlations. The correlations are designed for binary

interactions among the components CO, CO2, N2, H2, CH4 alcohols and

hydrocarbons. If a component is not CO, CO2, N2, H2, CH4 or an alcohol, it is

assumed to be a hydrocarbon.

Parameter Symbol Default MDS Lower Upper Units

Name/ Limit Limit

Element

TCLKP Tci TC x 5.0 2000.0 TEMPERATURE

PCLKP pci PC x PRESSURE

VOLUME

OMGLKP ωI OMEGA x -0.5 2.0 —

LKPZC Zci fcn(ω) (Method 1) x 0.1 0.5 —

fcn(pci,Vci,Tci)

(Method 2)

LKPKIJ kij fcn(TciVci / TcjVcj) x 5.0 5.0 —

Method 1 is the default for LKPZC; Method 2 can be invoked by setting the

value of LKPZC equal to zero.

Binary interaction parameters LKPKIJ are available for a large number of

components in the Aspen Physical Property System.

References

B.I. Lee and M.G. Kesler, AIChE J., Vol. 21, (1975) p. 510; errata: AIChE J.,

Vol. 21, (1975) p. 1040.

V. Plöcker, H. Knapp, and J.M. Prausnitz, Ind. Eng. Chem., Process Des. Dev.,

Vol. 17, (1978), p. 324.

The NBS/NRC Steam Tables are implemented like any other equation-of-state

in the Aspen Physical Property System. These steam tables can calculate any

thermodynamic property of water. The tables form the basis of the

STEAMNBS and STMNBS2 property methods. There are no parameter

requirements. They are the most accurate steam tables in the Aspen Physical

Property System. The STMNBS2 model uses the same equations as

STEAMNBS but with different root search method. The STEAMNBS method is

recommended for use with the SRK, BWRS, MXBONNEL and GRAYSON2

property methods.

References

L. Haar, J.S. Gallagher, and J.H. Kell, "NBS/NRC Steam Tables," (Washington:

Hemisphere Publishing Corporation, 1984).

Nothnagel

The Nothnagel equation-of-state calculates thermodynamic properties for the

vapor phase. It is used in property methods NRTL-NTH, UNIQ-NTH, VANL-

NTH, and WILS-NTH. It is recommended for systems that exhibit strong vapor

phase association. The model incorporates the chemical theory of

dimerization to account for strong association and solvation effects, such as

those found in organic acids, like acetic acid. The equation-of-state is:

Where:

b =

bij =

The chemical reaction for the general case of a mixture of dimerizing

components i and j is:

basis Kp is related to the true mole fractions and fugacity coefficients:

Where:

yi and yj = True mole fractions of monomers

yij = True mole fraction of dimer

ϕi = True fugacity coefficient of component i

Kij = Equilibrium constant for the dimerization of i and j, on a

pressure basis

When accounting for chemical reactions, the number of true species nt in the

mixture changes. The true molar volume V/nt is calculated from the

equation-of-state. Since both V and nt change in about the same proportion,

this number does not change much. However, the reported molar volume is

the total volume over the apparent number of species: V/na. Since the

apparent number of species is constant and the total volume decreases with

association, the quantity V/na reflects the apparent contraction in an

associating mixture.

The heat of reaction due to each dimerization can be calculated:

default the arithmetic mean of the heats of reaction for the dimerizations of

factor to this value:

The sum of the contributions of all dimerization reactions, corrected for the

ratio of apparent and true number of moles, is added to the molar enthalpy

departure:

or parameters you entered.

• Built-in correlations:

Physical Property System for many components.

Parameters you entered:

In this method, you enter Ai, Bi, Ci, and Di on the Properties Parameters

Unary.T-Dependent form. The units for Kii is pressure-1; use absolute units for

temperature. If you enter Kii and Kjj, then Kij is computed from

If you enter Ai, Bi, Ci, and Di, the equilibrium constants are computed using

the parameters you entered. Otherwise the equilibrium constants are

computed using built-in correlations.

Parameter Symbol Default Lower Upper Limit Units

Name/Element Limit

TC Tci — 5.0 2000.0 TEMPERATURE

TB Tbi — 4.0 2000.0 TEMPERATURE

5 8

PC pci — 10 10 PRESSURE

NTHA/1 bi 0.199 RTci / pci 0.01 1.0 MOLE-VOLUME

NTHA/2 di 0.33 0.01 3.0 —

Parameter Symbol Default Lower Upper Limit Units

Name/Element Limit

NTHA/3 pi 0 0.0 1.0 —

NTHK/1 Ai — — — PRESSURE

NTHK/2 Bi 0 — — TEMPERATURE

NTHK/3 Ci 0 — — TEMPERATURE

NTHK/4 Di 0 — — TEMPERATURE

†

NTHDDH 0 — — MOLE-

ENTHALPY

† For the following systems, the values given in Nothnagel et al., 1973 are

used by default:

• Methyl chloride/acetone

• Acetonitrile/acetaldehyde

• Acetone/chloroform

• Chloroform/diethyl amine

• Acetone/benzene

• Benzene/chloroform

• Chloroform/diethyl ether

• Chloroform/propyl formate

• Chloroform/ethyl acetate

• Chloroform/methyl acetate

• Chloroform/methyl formate

• Acetone/dichloro methane

• n-Butane/n-perfluorobutane

• n-Pentane/n-perfluoropentane

• n-Pentane/n-perfluorohexane

References

K.-H. Nothnagel, D. S. Abrams, and J.M. Prausnitz, "Generalized Correlation

for Fugacity Coefficients in Mixtures at Moderate Pressures," Ind. Eng. Chem.,

Process Des. Dev., Vol. 12, No. 1 (1973), pp. 25 – 35.

This section describes the Copolymer Perturbed-Chain Statistical Associating

Fluid Theory (PC-SAFT). This equation-of-state model is used through the PC-

SAFT property method.

The copolymer PC-SAFT represents the completed PC-SAFT EOS model

developed by Sadowski and co-workers (Gross and Sadowski, 2001, 2002a,

2002b; Gross et al., 2003; Becker et al., 2004; Kleiner et al., 2006). Unlike

the PC-SAFT EOS model (POLYPCSF) in Aspen Plus, the copolymer PC-SAFT

includes the association and polar terms and does not apply mixing rules to

calculate the copolymer parameters from its segments. Its applicability covers

fluid systems from small to large molecules, including normal fluids, water,

alcohols, and ketones, polymers and copolymers and their mixtures.

Copolymer PC-SAFT Fundamental Equations

The copolymer PC-SAFT model is based on the perturbation theory. The

underlying idea is to divide the total intermolecular forces into repulsive and

attractive contributions. The model uses a hard-chain reference system to

account for the repulsive interactions. The attractive forces are further divided

into different contributions, including dispersion, polar, and association.

Using a generated function, ψ, the copolymer PC-SAFT model in general can

be written as follows:

where ψhc, ψdisp, ψassoc, and ψpolar are contributions due to hard-chain fluids,

dispersion, association, and polarity, respectively.

where ares is the molar residual Helmholtz energy of mixtures, R is the gas

constant, T is the temperature, ρ is the molar density, and Zm is the

compressibility factor; ares is defined as:

where a is the Helmholtz energy of a mixture and aig is the Helmholtz energy

of a mixture of ideal gases at the same temperature, density and composition

xi. Once ψ is known, any other thermodynamic function of interest can be

easily derived. For instance, the fugacity coefficient ϕi is calculated as follows:

with

stated in the denominator, while all other mole fractions are considered

constant.

entropy, and Gibbs free energy can be obtained as follows:

Enthalpy departure:

Entropy departure:

In PC-SAFT model, a molecule is modeled as a chain molecule by a series of

freely-jointed tangent spheres. The contribution from hard-chain fluids as a

reference system consists of two parts, a nonbonding contribution (i.e., hard-

sphere mixtures prior to bonding to form chains) and a bonding contribution

due to chain formation:

where is the mean segment in the mixture, ψhs is the contribution from

hard-sphere mixtures on a per-segment basis, and ψchain is the contribution

due to chain formation. Both and ψhs are well-defined for mixtures

containing polymers, including copolymers; they are given by the following

equations:

where miα, σiα, and εiα are the segment number, the segment diameter, and

the segment energy parameter of the segment type α in the copolymer

component i, respectively. The segment number miα is calculated from the

segment ratio parameter riα:

where Miα is the total molecular weight of the segment type α in the

copolymer component i and can be calculated from the segment weight

fraction within the copolymer:

where wiα is the weight fraction of the segment type α in the copolymer

component i, and Mi is the molecular weight of the copolymer component i.

Following Sadowski and co-worker’s work (Gross et al., 2003; Becker et al.,

2004), the contribution from the chain connectivity can be written as follows:

with

where Biα,iβ is defined as the bonding fraction between the segment type α

and the segment type β within the copolymer component i, γ is the number of

the segment types within the copolymer component i, and ghsiα,jβ(diα,jβ) is the

radial distribution function of hard-sphere mixtures at contact.

start with a pure copolymer system which consists of only two different types

of segments α and β; this gives:

with

We now apply these equations to three common types of copolymers; a)

alternating, b) block, and c) random.

sequences. Therefore:

For a block copolymer, there is only one αβ pair and the number of αα and

ββ pairs depend on the length of each block; therefore:

the sequence is completely random, then the number of αβ adjacent pairs is

proportional to the product of the probabilities of finding a segment of type α

and a segment of type β in the copolymer. The probability of finding a

segment of type α is the fraction of segments zα in the copolymer:

set by Equation 2.70; the value for C is unity. Therefore:

A special case is the Sadowski’s model for random copolymer with two types

of segments only (Gross et al., 2003; Becker et al., 2004). In this model, the

bonding fractions are calculated as follows:

When zβ < zα

When zα < zβ

different segments to multi types of different segments γ within a copolymer

is straightforward.

For a generalized alternative copolymer, mα = mβ = ... = mr = m/γ ; there

are no adjacent sequences for the same type of segments. Therefore,

For a generalized block copolymer, there is only one pair for each adjacent

type of segment pairs (α ≠ β) and the number of pairs for a same type

depends on the length of the block; therefore:

statistical sense. If the sequence is completely random, then the number of

αβ adjacent pairs is proportional to the product of the probabilities of finding

a segment of type α and a segment of type β in the copolymer. The

probability of finding a segment of type α is the fraction of α segments zα in

the copolymer:

Therefore,

That is,

The equations for the dispersion term are given as follows:

where σiα,jβ and εiα,jβ are the cross segment diameter and energy parameters,

respectively; only one adjustable binary interaction parameter, κiα,jβ is

introduced to calculate them:

In above equations, the model constants a1i, a2i, a3i, b1i, b2i, and b3i are fitted

to pure-component vapor pressure and liquid density data of n-alkanes

(Gross and Sadowski, 2001).

Model

The association term in PC-SAFT model in general needs an iterative

procedure to calculate the fraction of a species (solvent or segment) that are

bounded to each association-site type. Only in pure or binary systems, the

fraction can be derived explicitly for some specific models. We start with

general expressions for the association contribution for copolymer systems as

follows:

number of the association-site type A on the segment type α in the

copolymer component i, and is the mole fraction of the segment type α

in the copolymer component i that are not bonded with the association-site

type A; it can be estimated as follows:

with

where is the cross effective association volume and is the

cross association energy; they are estimated via simple combination rules:

association energy between the association-site types A and B, of the

segment type α in the copolymer component i, respectively.

The association-site number of the site type A on the segment type α in the

copolymer component i is equal to the number of the segment type α in the

copolymer component i,

where Niα is the number of the segment type α in the copolymer component i

and Mα is the molecular weight of the segment type α. In other words, the

association-site number for each site type within a segment is the same;

therefore, we can rewrite the equations above as follows:

association-site type associated with a species in a component. In practice,

further assumption is needed for efficiency. The commonly used model is the

so-called 2B model (Huang and Radosz, 1990). It assumes that an associating

species (solvent or segment) has two association sites, one is designed as the

site type A and another as the site type B. Similarly to the hydrogen bonding,

type A treats as a donor site with positive charge and type B as an acceptor

site with negative charge; only the donor-acceptor association bonding is

permitted and this concept applies to both pure systems (self-association

such as water) and mixtures (both self-association and cross-association such

as water-methanol). Therefore, we can rewrite these equations as follows:

It is easy to show that

Therefore

The equations for the polar term are given by Jog et al. (2001) as follows:

In the above equations, I2(η) and I3(η) are the pure fluid integrals and μiα

and (xp)iα are the dipole moment and dipolar fraction of the segment type α

Rushbrooke et al. (1973) have shown that

Reference

Jog, P. K., Sauer, S. G., Blaesing, J., & Chapman, W. G. (2001), Application

of Dipolar Chain Theory to the Phase Behavior of Polar Fluids and Mixtures.

Ind. Eng. Chem. Res., 40, 4641.

Rushbrooke, G. S., & Stell, G., Hoye, J. S. (1973), Molec. Phys., 26, 1199.

Pure parameters

Each non-association species (solvent or segment) must have a set of three

pure-component parameter; two of them are the segment diameter σ and the

segment energy parameter ε. The third parameter for a solvent is the

segment number m and for a segment is the segment ratio parameter r. For

an association species, two additional parameters are the effective association

volume κ(AB) and the association energy ε(AB). For a polar species, two

additional parameters are the dipole moment μ and the segment dipolar

fraction xp.

Binary parameters

There are three types of binary interactions in copolymer systems: solvent-

solvent, solvent-segment, and segment-segment. The binary interaction

parameter κiα,jβ allows complex temperature dependence:

with

The following table lists the copolymer PC-SAFT EOS model parameters

implemented in Aspen Plus:

Parameter Symbol Default Lower Upper MDS Units Comments

Name/ Limit Limit Keyword

Element

PCSFTM m — — — X — Unary

PCSFTV σ — — — X — Unary

PCSFTU ε/k — — — X TEMP Unary

PCSFTR r — — — X — Unary

PCSFAU εAB/k — — — X TEMP Unary

MOMENT

PCSFXP xp — — — X — Unary

PCSKIJ/1 aiα,jβ 0.0 — — X — Binary,

Symmetric

PCSKIJ/2 biα,jβ 0.0 — — X — Binary,

Symmetric

PCSKIJ/3 ciα,jβ 0.0 — — X — Binary,

Symmetric

PCSKIJ/4 diα,jβ 0.0 — — X — Binary,

Symmetric

PCSKIJ/5 eiα,jβ 0.0 — — X — Binary,

Symmetric

PCSKIJ/6 Tref 298.15 — — X TEMP Binary,

Symmetric

Parameter Input and Regression for Copolymer

PC-SAFT

Since the copolymer PC-SAFT is built based on the segment concept, the

unary (pure) parameters must be specified for a solvent or a segment.

Specifying a unary parameter for a polymer component (homopolymer or

copolymer) will be ignored by the simulation. For a non-association and non-

polar solvent, three unary parameters PCSFTM, PCSFTU, and PCSFTV must be

specified. For a non-association and non-polar segment, these three unary

parameters PCSFTR, PCSFTU, and PCSFTV must be specified. For an

association species (solvent or segment), two additional unary parameters

PCSFAU and PCSFAV must be specified. For a polar species (solvent or

segment), two additional unary parameters PCSFMU and PCSFXP must be

specified.

The binary parameter PCSKIJ can be specified for each solvent-solvent pair,

or each solvent-segment pair, or each segment-segment pair. By default, the

binary parameter is set to be zero.

A databank called PC-SAFT contains both unary and binary PC-SAFT

parameters available from literature; it must be used with the PC-SAFT

property method. The unary parameters available for segments are stored in

the SEGMENT databank. If unary parameters are not available for a species

(solvent or segment) in a calculation, the user can perform an Aspen Plus

Data Regression Run (DRS) to obtain unary parameters. For non-polymer

components (mainly solvents), the unary parameters are usually obtained by

fitting experimental vapor pressure and liquid molar volume data. To obtain

unary parameters for a segment, experimental data on liquid density of the

homopolymer that is built by the segment should be regressed. Once the

unary parameters are available for a segment, the ideal-gas heat capacity

parameter CPIG may be regressed for the same segment using experimental

liquid heat capacity data for the same homopolymer. In addition to unary

parameters, the binary parameter PCSKIJ for each solvent-solvent pair, or

each solvent-segment pair, or each segment-segment pair, can be regressed

using vapor-liquid equilibrium (VLE) data in the form of TPXY data in Aspen

Plus.

OLIGOMER type, and the number of the segment that builds the oligomer

must be specified.

Peng-Robinson

The Peng-Robinson equation-of-state is the basis for the PENG-ROB and PR-

BM property methods. The model has been implemented with choices of

different alpha functions (see Peng-Robinson Alpha Functions) and has been

extended to include advanced asymmetric mixing rules.

Note: You can choose any of the available alpha functions, but you cannot

define multiple property methods based on this model using different alpha

functions within the same run.

By default, the PENG-ROB property method uses the literature version of the

alpha function and mixing rules. The PR-BM property method uses the

Boston-Mathias alpha function and standard mixing rules. These default

property methods are recommended for hydrocarbon processing applications

such as gas processing, refinery, and petrochemical processes. Their results

are comparable to those of the property methods that use the standard

Redlich-Kwong-Soave equation-of-state.

When advanced alpha function and asymmetric mixing rules are used with

appropriately obtained parameters, the Peng-Robinson model can be used to

accurately model polar, non-ideal chemical systems. Similar capability is also

available for the Soave-Redlich-Kwong model.

The equation for the Peng-Robinson model is:

Where:

b =

c =

a = a0+a1

a0 =

been made temperature-dependent)

kij =

kij = kji

a1

highly non-linear systems)

lij =

In general, .

ai =

bi =

ci =

For best results, the binary parameters kij and lij must be determined from

regression of phase equilibrium data such as VLE data. The Aspen Physical

Property System also has built-in kij and lij for a large number of component

pairs in the EOS-LIT databank. These parameters are used automatically with

the PENG-ROB property method. Values in the databank can be different than

those used with other models such as Soave-Redlich-Kwong or Redlich-

Kwong-Soave, and this can produce different results.

The model has option codes which can be used to customize the model, by

selecting a different alpha function and other model options. See Peng-

Robinson Alpha Functions for a description of the alpha functions. See Option

Codes for Equation of State Models (under ESPR) for a list of the option

codes.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

PRTC Tci TC x 5.0 2000.0 TEMPERATURE

5 8

PRPC pci PC x 10 10 PRESSURE

OMGPR ωi OMEGA x -0.5 2.0 —

PRKBV/1 kij(1) 0 x — — —

PRKBV/2 kij(2) 0 x — — TEMPERATURE

PRKBV/3 kij(3) 0 x — — TEMPERATURE

PRKBV/4 Tlower 0 x — — TEMPERATURE

PRKBV/5 Tupper 1000 x — — TEMPERATURE

PRLIJ/1 lij(1) 0 x — — —

PRLIJ/2 lij(2) 0 x — — TEMPERATURE

PRLIJ/3 lij(3) 0 x — — TEMPERATURE

PRLIJ/4 Tlower 0 x — — TEMPERATURE

PRLIJ/5 Tupper 1000 x — — TEMPERATURE

References

D.-Y. Peng and D. B. Robinson, "A New Two-Constant Equation-of-state," Ind.

Eng. Chem. Fundam., Vol. 15, (1976), pp. 59–64.

P.M. Mathias, H.C. Klotz, and J.M. Prausnitz, "Equation of state mixing rules

for multicomponent mixtures: the problem of invariance," Fluid Phase

Equilibria, Vol 67, (1991), pp. 31-44.

Standard Peng-Robinson

The Standard Peng-Robinson equation-of-state is the original formulation of

the Peng-Robinson equation of state with the standard alpha function (see

Peng-Robinson Alpha Functions). It is recommended for hydrocarbon

processing applications such as gas processing, refinery, and petrochemical

processes. Its results are comparable to those of the standard Redlich-

Kwong-Soave equation of state.

Note: You can choose any of the available alpha functions, but you cannot

define multiple property methods based on this model using different alpha

functions within the same run.

The equation for this model is:

Where:

b =

a =

ai =

bi =

kij =

The model has option codes which can be used to customize the model, by

selecting a different alpha function and other model options. See Peng-

Robinson Alpha Functions for a description of the alpha functions. See Option

Codes for Equation of State Models (under ESPRSTD) for a list of the option

codes.

For best results, the binary parameter kij must be determined from regression

of phase equilibrium data such as VLE data. The Aspen Physical Property

System also has built-in kij for a large number of component pairs in the EOS-

LIT databank. These parameters are used automatically with the PENG-ROB

property method. Values in the databank can be different than those used

with other models such as Soave-Redlich-Kwong or Redlich-Kwong-Soave,

and this can produce different results.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

TCPRS Tci TC x 5.0 2000.0 TEMPERATURE

PCPRS pci PC x 105 108 PRESSURE

OMGPRS ωi OMEGA x -0.5 2.0 —

PRKBV/1 kij(1) 0 x - - -

PRKBV/2 kij(2) 0 x - - TEMPERATURE

PRKBV/3 kij(3) 0 x - - TEMPERATURE

PRKBV/4 Tlower 0 x - - TEMPERATURE

PRKBV/5 Tupper 1000 x - - TEMPERATURE

References

D.-Y. Peng and D. B. Robinson, "A New Two-Constant Equation-of-state," Ind.

Eng. Chem. Fundam., Vol. 15, (1976), pp. 59–64.

Peng-Robinson-MHV2

This model uses the Peng-Robinson equation-of-state for pure compounds.

The mixing rules are the predictive MHV2 rules. Several alpha functions can

be used in the Peng-Robinson-MHV2 equation-of-state model for a more

accurate description of the pure component behavior. The pure component

behavior and parameter requirements are described in Standard Peng-

Robinson, or in Peng-Robinson Alpha Functions.

The MHV2 mixing rules are an example of modified Huron-Vidal mixing rules.

A brief introduction is provided in Huron-Vidal Mixing Rules. For more details,

see MHV2 Mixing Rules.

This model uses the Redlich-Kwong-Soave equation-of-state for pure

compounds. The mixing rules are the predictive Holderbaum rules, or PSRK

method. Several alpha functions can be used in the PSRK equation-of-state

model for a more accurate description of the pure component behavior. The

pure component behavior and parameter requirements are described in

Standard Redlich-Kwong-Soave and in Soave Alpha Functions.

Note: You can choose any of the available alpha functions, but you cannot

define multiple property methods based on this model using different alpha

functions within the same run.

The PSRK method is an example of modified Huron-Vidal mixing rules. A brief

introduction is provided in Huron-Vidal Mixing Rules. For more details, see

Predictive Soave-Redlich-Kwong-Gmehling Mixing Rules.

Peng-Robinson-Wong-Sandler

This model uses the Peng-Robinson equation-of-state for pure compounds.

The mixing rules are the predictive Wong-Sandler rules. Several alpha

functions can be used in the Peng-Robinson-Wong-Sandler equation-of-state

model for a more accurate description of the pure component behavior. The

pure component behavior and parameter requirements are described in Peng-

Robinson, and in Peng-Robinson Alpha Functions.

Note: You can choose any of the available alpha functions, but you cannot

define multiple property methods based on this model using different alpha

functions within the same run.

The Wong-Sandler mixing rules are an example of modified Huron-Vidal

mixing rules. A brief introduction is provided in Huron-Vidal Mixing Rules. For

more details see Wong-Sandler Mixing Rules., this chapter.

Redlich-Kwong

The Redlich-Kwong equation-of-state can calculate vapor phase

thermodynamic properties for the following property methods: NRTL-RK,

UNIFAC, UNIF-LL, UNIQ-RK, VANL-RK, and WILS-RK. It is applicable for

systems at low to moderate pressures (maximum pressure 10 atm) for which

the vapor-phase nonideality is small. The Hayden-O'Connell model is

recommended for a more nonideal vapor phase, such as in systems

containing organic acids. It is not recommended for calculating liquid phase

properties.

The equation for the model is:

p =

Where:

=

b =

ai =

bi =

Name/Element Limit Limit

TC Tci — — 5.0 2000.0 TEMPERATURE

5 8

PC pci — — 10 10 PRESSURE

References

O. Redlich and J.N.S. Kwong, "On the Thermodynamics of Solutions V. An

Equation-of-state. Fugacities of Gaseous Solutions," Chem. Rev., Vol. 44,

(1979), pp. 223 – 244.

Redlich-Kwong-Aspen

The Redlich-Kwong-Aspen equation-of-state is the basis for the RK-ASPEN

property method. It can be used for hydrocarbon processing applications. It is

also used for more polar components and mixtures of hydrocarbons, and for

light gases at medium to high pressures.

The equation is the same as Redlich-Kwong-Soave:

p =

a =

b =

ai =

bi =

ka,ij =

kb,ij =

For best results, binary parameters kij must be determined from phase-

equilibrium data regression, such as VLE data.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

TCRKA Tci TC x 5.0 2000.0 TEMPERATURE

PCRKA pci PC x 105 108 PRESSURE

OMGRKA ωi OMEGA x -0.5 2.0 —

RKAKA1 ka,ij1 0 x -15.0 15.0 TEMPERATURE

RKAKB0 kb,ij0 0 x -5.0 5.0 —

RKAKB1 kb,ij1 0 x -15.0 15.0 TEMPERATURE

References

Mathias, P.M., "A Versatile Phase Equilibrium Equation-of-state", Ind. Eng.

Chem. Process Des. Dev., Vol. 22, (1983), pp. 385 – 391.

Redlich-Kwong-Soave

This is the standard Redlich-Kwong-Soave equation-of-state, and is the basis

for the RK-SOAVE property method. It is recommended for hydrocarbon

processing applications, such as gas-processing, refinery, and petrochemical

processes. Its results are comparable to those of the Peng-Robinson

equation-of-state.

The equation is:

Where:

b =

ai =

bi =

kij = kji

; ;

The parameter ai is calculated according to the standard Soave formulation

(see Soave Alpha Functions, equations 1, 2, 3, 5, and 6).

Note: You can choose any of the available alpha functions, but you cannot

define multiple property methods based on this model using different alpha

functions within the same run.

The model uses option codes which are described in Soave-Redlich-Kwong

Option Codes.

For best results, binary parameters kij must be determined from phase-

equilibrium data regression (for example, VLE data). The Aspen Physical

Property System also has built-in kij for a large number of component pairs in

the EOS-LIT databank. These binary parameters are used automatically with

the RK-SOAVE property method. Values of kij in the databank can be different

than those used with other models such as Soave-Redlich-Kwong or Standard

Peng-Robinson, and this can produce different results.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

TCRKSS Tci TC x 5.0 2000.0 TEMPERATURE

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

PCRKSS pci PC x 105 108 PRESSURE

OMRKSS ωi OMEGA x -0.5 2.0 —

RKSKBV/2 kij(2) 0 x — — TEMPERATURE

RKSKBV/3 kij(3) 0 x — — TEMPERATURE

RKSKBV/4 Tk,lower 0 x — — TEMPERATURE

RKSKBV/5 Tk,upper 1000 x — — TEMPERATURE

RKSLBV/1 lij(1) 0 x — — —

RKSLBV/2 lij(2) 0 x — — TEMPERATURE

RKSLBV/3 lij(3) 0 x — — TEMPERATURE

RKSLBV/4 Tl,lower 0 x — — TEMPERATURE

RKSLBV/5 Tl,upper 1000 x — — TEMPERATURE

References

G. Soave, "Equilibrium Constants for Modified Redlich-Kwong Equation-of-

state," Chem. Eng. Sci., Vol. 27, (1972), pp. 1196 – 1203.

J. Schwartzentruber and H. Renon, "Extension of UNIFAC to High Pressures

and Temperatures by the Use of a Cubic Equation-of-state," Ind. Eng. Chem.

Res., Vol. 28, (1989), pp. 1049 – 1955.

A. Peneloux, E. Rauzy, and R. Freze, "A Consistent Correction For Redlich-

Kwong-Soave Volumes", Fluid Phase Eq., Vol. 8, (1982), pp. 7–23.

Redlich-Kwong-Soave-Boston-Mathias

The Redlich-Kwong-Soave-Boston-Mathias equation-of-state is the basis for

the RKS-BM property method. It is the Redlich-Kwong-Soave equation-of-

state with the Boston-Mathias alpha function (see Soave Alpha Functions). It

is recommended for hydrocarbon processing applications, such as gas-

processing, refinery, and petrochemical processes. Its results are comparable

to those of the Peng-Robinson-Boston-Mathias equation-of-state.

Note: You can choose any of the available alpha functions, but you cannot

define multiple property methods based on this model using different alpha

functions within the same run.

The equation is:

p =

Where:

a1 is an additional, asymmetric (polar) term:

b =

ai =

bi =

kij = kji

; ;

The parameter ai is calculated by the standard Soave formulation at

supercritical temperatures. If the component is supercritical, the Boston-

Mathias extrapolation is used (see Soave Alpha Functions).

The model uses option codes which are described in Soave-Redlich-Kwong

Option Codes.

For best results, binary parameters kij must be determined from phase-

equilibrium data regression (for example, VLE data).

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

TCRKS Tci TC x 5.0 2000.0 TEMPERATURE

PCRKS pci PC x 105 108 PRESSURE

OMGRKS ωi OMEGA x -0.5 2.0 —

RKSKBV/2 kij(2) 0 x — — TEMPERATURE

RKSKBV/3 kij(3) 0 x — — TEMPERATURE

RKSKBV/4 Tk,lower 0 x — — TEMPERATURE

RKSKBV/5 Tk,upper 1000 x — — TEMPERATURE

RKSLBV/1 lij(1) 0 x — — —

RKSLBV/2 lij(2) 0 x — — TEMPERATURE

RKSLBV/3 lij(3) 0 x — — TEMPERATURE

RKSLBV/4 Tl,lower 0 x — — TEMPERATURE

RKSLBV/5 Tl,upper 1000 x — — TEMPERATURE

References

G. Soave, "Equilibrium Constants for Modified Redlich-Kwong Equation-of-

state," Chem. Eng. Sci., Vol. 27, (1972), pp. 1196 – 1203.

Redlich-Kwong-Soave-Wong-Sandler

This equation-of-state model uses the Redlich-Kwong-Soave equation-of-state

for pure compounds. The predictive Wong-Sandler mixing rules are used.

Several alpha functions can be used in the Redlich-Kwong-Soave-Wong-

Sandler equation-of-state model for a more accurate description of the pure

component behavior. The pure component behavior and parameter

requirements are described in Standard Redlich-Kwong-Soave, and in Soave

Alpha Functions.

Note: You can choose any of the available alpha functions, but you cannot

define multiple property methods based on this model using different alpha

functions within the same run.

The Wong-Sandler mixing rules are an example of modified Huron-Vidal

mixing rules. A brief introduction is provided in Huron-Vidal Mixing Rules. For

more details, see Wong-Sandler Mixing Rules.

Redlich-Kwong-Soave-MHV2

This equation-of-state model uses the Redlich-Kwong-Soave equation-of-state

for pure compounds. The predictive MHV2 mixing rules are used. Several

alpha functions can be used in the RK-Soave-MHV2 equation-of-state model

for a more accurate description of the pure component behavior. The pure

component behavior and its parameter requirements are described in

Standard Redlich-Kwong-Soave, and in Soave Alpha Functions.

Note: You can choose any of the available alpha functions, but you cannot

define multiple property methods based on this model using different alpha

functions within the same run.

The MHV2 mixing rules are an example of modified Huron-Vidal mixing rules.

A brief introduction is provided in Huron-Vidal Mixing Rules. For more details,

see MHV2 Mixing Rules.

Schwartzentruber-Renon

The Schwartzentruber-Renon equation-of-state is the basis for the SR-POLAR

property method. It can be used to model chemically nonideal systems with

the same accuracy as activity coefficient property methods, such as the

WILSON property method. This equation-of-state is recommended for highly

non-ideal systems at high temperatures and pressures, such as in methanol

synthesis and supercritical extraction applications.

The equation for the model is:

p =

Where:

a =

b =

c =

ai =

bi =

ci =

ka,ij =

lij =

kb,ij =

ka,ij = ka,ji

lij = -lji

kb,ij = kb,ji

The binary parameters ka,ij, kb,ij, and lij are temperature-dependent. In most

cases, ka,ij0 and lij0 are sufficient to represent the system of interest.

VLE calculations are independent of c. However, c does influence the fugacity

values and can be adjusted to (liquid) molar volumes. For a wide temperature

range, adjust cio to the molar volume at 298.15K or at boiling temperature.

Warning: Using c1i and c2i can cause anomalous behavior in enthalpy and

heat capacity. Their use is strongly discouraged.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

TCRKU Tci TC x 5.0 2000.0 TEMPERATURE

PCRKU pci PC x 105 108 PRESSURE

OMGRKU ωi OMEGA x -0.5 2.0 —

RKUPP0 †† q0i — x — — —

RKUPP1 †† q1i 0 x — — —

RKUPP2 †† q2i 0 x — — —

RKUC0 c0i 0 x — — —

RKUC1 c1i 0 x — — —

RKUC2 c2i 0 x — — —

RKUKA0 ††† ka,ij0 0 x — — —

RKUKA1 ††† ka,ij1 0 x — — TEMPERATURE

RKUKA2 ††† ka,ij2 0 x — — TEMPERATURE †

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

RKULA0 ††† lij0 0 x — — —

RKULA1 ††† lij1 0 x — — TEMPERATURE

RKULA2 ††† lij2 0 x — — TEMPERATURE †

RKUKB0 ††† kb,ij0 0 x — — —

RKUKB1 ††† kb,ij1 0 x — — TEMPERATURE

RKUKB2 ††† kb,ij2 0 x — — TEMPERATURE †

† Absolute temperature units are assumed for ka,ij2, lij2, and kb,ij2.

†† For polar components (dipole moment >> 0), if you do not enter q0i, the

system estimates q0i, q1i, q2i from vapor pressures using the Antoine vapor

pressure model.

††† If you do not enter at least one of the binary parameters ka,ij0, ka,ij2, lij0,

lij2, kb,ij0, or kb,ij2 the system estimates ka,ij0, ka,ij2, lij0, and lij2 from the UNIFAC

or Hayden O'Connell models.

References

G. Soave, "Equilibrium Constants for Modified Redlich-Kwong Equation-of-

state," Chem. Eng. Sci., Vol. 27, (1972), pp. 1196 - 1203.

J. Schwartzentruber and H. Renon, "Extension of UNIFAC to High Pressures

and Temperatures by the Use of a Cubic Equation-of-State," Ind. Eng. Chem.

Res., Vol. 28, (1989), pp. 1049 – 1955.

A. Peneloux, E. Rauzy, and R. Freze, "A Consistent Correction For Redlich-

Kwong-Soave Volumes", Fluid Phase Eq., Vol. 8, (1982), pp. 7–23.

Soave-Redlich-Kwong

The Soave-Redlich-Kwong equation-of-state is the basis of the SRK property

method. This model is based on the same equation of state as the Redlich-

Kwong-Soave model. However, this model has several important differences.

• A volume translation concept introduced by Peneloux and Rauzy is used to

improve molar liquid volume calculated from the cubic equation of state.

• Improvement in water properties is achieved by using the NBS Steam

Table.

• Improvement in speed of computation for equation based calculation is

achieved by using composition independent fugacity.

• Optional Kabadi-Danner mixing rules for improved phase equilibrium

calculations in water-hydrocarbon systems (see SRK-Kabadi-Danner)

• Optional Mathias alpha function

Note: You can choose any of the available alpha functions, but you cannot

define multiple property methods based on this model using different alpha

functions within the same run.

This equation-of-state can be used for hydrocarbon systems that include the

common light gases, such as H2S, CO2 and N2.

The form of the equation-of-state is:

Where:

Where:

;

a1 is an additional, asymmetric (polar) term:

Where:

; ;

The enthalpy, entropy, Gibbs energy, and molar volume of water are

calculated from the steam tables. The total properties are mole-fraction

averages of these values with the properties calculated by the equation of

state for other components. Fugacity coefficient is not affected.

For best results, the binary parameter kij must be determined from phase

equilibrium data regression (for example, VLE data). The Aspen Physical

Property System also has built-in kij for a large number of component pairs in

the SRK-ASPEN databank. These parameters are used automatically with the

SRK property method. Values of kij in the databank can be different than

those used with other models such as Standard Redlich-Kwong-Soave or

Standard Redlich-Kwong-Soave, and this can produce different results.

The model uses option codes which are described in Soave-Redlich-Kwong

Option Codes.

Parameter Symbol Default MDS Lower Upper Units

Name/ Limit Limit

Element

SRKTC Tci TC x 5.0 2000.0 TEMPERATURE

SRKOMG ωi OMEGA x –0.5 2.0 —

SRKKIJ/1 kij(1) 0 x — — —

SRKKIJ/2 kij(2) 0 x — — TEMPERATURE

SRKKIJ/3 kij(3) 0 x — — TEMPERATURE

SRKKIJ/4 Tlower 0 x — — TEMPERATURE

SRKKIJ/5 Tupper 1000 x — — TEMPERATURE

SRKLIJ/1 lij(1) 0 x — — —

SRKLIJ/2 lij(2) 0 x — — TEMPERATURE

SRKLIJ/3 lij(3) 0 x — — TEMPERATURE

SRKLIJ/4 Tlower 0 x — — TEMPERATURE

SRKLIJ/5 Tupper 1000 x — — TEMPERATURE

References

G. Soave, "Equilibrium Constants for Modified Redlich-Kwong Equation-of-

state," Chem. Eng. Sci., Vol. 27, (1972), pp. 1196 - 1203.

A. Peneloux, E. Rauzy, and R. Freze, "A Consistent Correction For Redlich-

Kwong-Soave Volumes", Fluid Phase Eq., Vol. 8, (1982), pp. 7–23.

P.M. Mathias, H.C. Klotz, and J.M. Prausnitz, "Equation of state mixing rules

for multicomponent mixtures: the problem of invariance," Fluid Phase

Equilibria, Vol 67, (1991), pp. 31-44.

SRK-Kabadi-Danner

The SRK-Kabadi-Danner property model uses the SRK equation-of-state with

improved phase equilibrium calculations for mixtures containing water and

hydrocarbons. These improvements are achieved by using the Kabadi-Danner

mixing rules.

The form of the equation-of-state is:

Where:

Where:

;

The best values of kwj (w = water) were obtained from experimental data.

Results are given for seven homologous series.

with Water

Homologous series kwj

Alkanes 0.500

Alkenes 0.393

Dialkenes 0.311

Acetylenes 0.348

Naphthenes 0.445

Cycloalkenes 0.355

Aromatics 0.315

Where:

molecule of hydrocarbon i.

Contribution Parameters

Group l gl , atm m6 x 105

CH4 1.3580

– CH3 0.9822

– CH2 – 1.0780

> CH – 0.9728

>C< 0.8687

– CH2 – (cyclic) 0.7488

> CH – (cyclic) 0.7352

– CH = CH – (cyclic) † 0.6180

Group l gl , atm m6 x 105

CH2 = CH2 1.7940

CH2 = CH – 1.3450

CH2 = C< 0.9066

CH ≡ CH 1.6870

CH ≡ C – 1.1811

– CH = 0.5117

> C = (aromatic) 0.3902

† This value is obtained from very little data. Might not be reliable.

The model uses option codes which are described in Soave-Redlich-Kwong

Option Codes.

SRK-Kabadi-Danner uses the same parameters as SRK, with added

interaction parameters. Do not specify values for the SRKLIJ parameters

when using SRK-KD.

Parameter Symbol Default MDS Lower Upper Units

Name/ Limit Limit

Element

SRKTC Tci TC x 5.0 2000.0 TEMPERATURE

SRKOMG ωi OMEGA x –0.5 2.0 —

SRKWF Gi 0 x — — —

SRKZRA zRA RKTZRA x — — —

SRKKIJ/1 kij(1) 0 x — — —

SRKKIJ/2 kij(2) 0 x — — TEMPERATURE

SRKKIJ/3 kij(3) 0 x — — TEMPERATURE

SRKKIJ/4 Tlower 0 x — — TEMPERATURE

SRKKIJ/5 Tupper 0 x — — TEMPERATURE

References

V. Kabadi and R. P. Danner, "A Modified Soave-Redlich-Kwong Equation of

State for Water-Hydrocarbon Phase Equilibria", Ind. Eng. Chem. Process Des.

Dev., Vol. 24, No. 3, (1985), pp. 537-541.

SRK-ML

The SRK-ML property model is the same as the standard Soave-Redlich-

Kwong model with two exceptions:

• kij does not equal kji for non-ideal systems; they are unsymmetric, and a

different set of parameters is used, as shown below.

• The lij are calculated from the equation lij = kji - kij

Parameter Symbol Default MDS Lower Upper Units

Name/ Limit Limit

Element

SRKTCML Tci TC x 5.0 2000.0 TEMPERATURE

SRKOMGML ωi OMEGA x –0.5 2.0 —

SRKKIJML/1 kij(1) 0 x — — —

SRKKIJML/2 kij(2) 0 x — — TEMPERATURE

SRKKIJML/3 kij(3) 0 x — — TEMPERATURE

SRKKIJML/4 Tlower 0 x — — TEMPERATURE

SRKKIJML/5 Tupper 1000 x — — TEMPERATURE

VPA/IK-CAPE Equation-of-State

The VPA/IK-CAPE equation of state is similar to the HF equation of state but

allows dimerization, tetramerization and hexamerization to occur

simultaneously. The main assumption of the model is that only molecular

association causes the gas phase nonideality. Attractive forces between the

molecules and the complexes are neglected.

There are three kinds of associations, which can be modeled:

• Dimerization (examples: formic acid, acetic acid)

• Tetramerization (example: acetic acid)

• Hexamerization (example: hydrogen fluoride)

To get the largest possible flexibility of the model all these kinds of

association can occur simultaneously, for example, in a mixture containing

acetic acid and HF. Up to five components can associate, and any number of

inert components are allowed. This is the only difference between this model

and the HF equation of state, which account only the hexamerization of HF.

Symbols

In the following description, these symbols are used:

yi = Apparent concentration

zin = True concentration, for component i and degree of

association n=1, 2, 4, 6

and j, for i,j 1 to 5.

p0 = Reference pressure

k = Number of components

Association Equilibria

Every association equilibrium reaction

(1)

(2)

(3)

(4)

By setting

(5)

(6)

To evaluate the true concentration of every complex zin, the following

nonlinear systems of equations are to be solved:

Total mass balance:

The sum of true concentrations is unity.

(7)

The ratio of the monomers of each component i>1 and component i=1

occurring in the various complexes must be equal to the ratio of their

apparent concentrations.

(8)

developed. After having solved it, all the zin and zMij can be determined using

equations (3, 4). This is the main step to evaluate all the properties needed

for a calculation.

The compressibility factor is defined by the ratio between the number of

complexes and the number of monomers in the complexes.

(9)

(10)

Fugacity Coefficient

As is well-known from thermodynamics, the fugacity coefficient can be

calculated by

(11)

According to the ASPEN enthalpy model, an equation of state must supply an

expression to compute the isothermal molar enthalpy departure between zero

pressure and actual pressure. In the following section this enthalpy

contribution per mole monomers is abbreviated by Δha.

Taking this sort of gas phase non-ideality into account, the specific enthalpy

per mole can be written as

(12)

with

(13)

complexes is considered. The quota of monomers i being integrated in a

complex of degree n is given by

(14)

and

(16)

(1)

(2)

(17)

(18)

(19)

For each monomer being integrated in a complex of degree n, its contribution

to the enthalpy departure is Δhin / n or ΔhMij / 2, respectively. Hence, Δha can

easily be derived by

(20)

A similar expression for Δga should hold as it does for the enthalpy departure

(eq. 20):

(21)

using

(22)

and

(23)

(24)

Using the association model, more different species occur than can be

distinguished. Thus, the equivalent expression for the entropy of mixing

should be written with the true concentrations. As eq. 24 refers to 1 mole

monomers, the expression should be weighted by the compressibility factor

representing the true number of moles. The new expression is

(25)

(26)

and, analogously,

(27)

Name/Element Limit Limit

DMER/1 Ai2 0 X – – –

DMER/2 Bi2 0 X – – TEMPERATURE

TMER/1 Ai4 0 X – – –

TMER/2 Bi4 0 X – – TEMPERATURE

HMER/1 Ai6 0 X – – –

HMER/2 Bi6 0 X – – TEMPERATURE

References

M. M. Abbott and H. C. van Ness, "Thermodynamics of Solutions Containing

Reactive Species, a Guide to Fundamentals and Applications," Fluid Phase Eq.,

Vol. 77, (1992) pp. 53–119.

V. V. De Leeuw and S. Watanasiri, "Modeling Phase Equilibria and Enthalpies

of the System Water and Hydrofluoric Acid Using an HF Equation-of-state in

Conjunction with the Electrolyte NRTL Activity Coefficient Model," Paper

Presented at the 13th European Seminar on Applied Thermodynamics, June

9–12, Carry-le-Rouet, France, 1993.

R. W. Long, J. H. Hildebrand, and W. E. Morrell, "The Polymerization of

Gaseous Hydrogen and Deuterium Fluorides," J. Am. Chem. Soc., Vol. 65,

(1943), pp. 182–187.

C. E. Vanderzee and W. Wm. Rodenburg, "Gas Imperfections and

Thermodynamic Excess Properties of Gaseous Hydrogen Fluoride," J. Chem.

Thermodynamics, Vol. 2, (1970), pp. 461–478.

The pure component parameters for the Peng-Robinson equation-of-state are

calculated as follows:

(1)

(2)

equation-of-state under these conditions:

(3)

Soave in the Redlich-Kwong equation-of-state. This parameter improves the

correlation of the pure component vapor pressure.

Note: You can choose any of the alpha functions described here, but you

cannot define multiple property methods based on this model using different

alpha functions within the same run.

This approach was also adopted by Peng and Robinson:

(4)

acentric factor:

(5)

Peng-Robinson alpha function is adequate for hydrocarbons and other

nonpolar compounds, but is not sufficiently accurate for polar compounds.

temperature units.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

TCPR Tci TC X 5.0 2000.0 TEMPERATURE

5 8

PCPR pci PC X 10 10 PRESSURE

OMGPR ωi OMEGA X -0.5 2.0 —

Boston-Mathias Extrapolation

For light gases at high reduced temperatures (> 5), equation 4 gives

unrealistic results. The boundary conditions are that attraction between

molecules should vanish for extremely high temperatures, and α reduces

asymptotically to zero. Boston and Mathias derived an alternative function for

temperatures higher than critical:

(6)

With

=

temperatures. Additional parameters are not needed.

The extended Gibbons-Laughton alpha function is suitable for use with both

polar and nonpolar components. It has the flexibility to fit the vapor pressure

of most substances from the triple point to the critical point.

parameters.

This function is equivalent to the standard Peng-Robinson alpha function if

Name/Element Limit Limit

PRGLP/1 X — X — — —

PRGLP/2 Y 0 X — — —

PRGLP/3 Z 0 X — — —

PRGLP/4 n 2 X — — —

PRGLP/5 Tlower 0 X — — TEMPERATURE

PRGLP/6 Tupper 1000 X — — TEMPERATURE

The Twu generalized alpha function is a theoretically-based function that is

currently recognized as the best available alpha function. It behaves better

than other functions at supercritical conditions (T > Tc) and when the acentric

factor is large. The improved behavior at high values of acentric factor is

important for high molecular weight pseudocomponents. There is no limit on

the minimum value of acentric factor that can be used with this function.

Where the L, M, and N are parameters that vary depending on the equation of

state and whether the temperature is above or below the critical temperature

of the component.

For Peng-Robinson equation of state:

Subcritical T Supercritical T

L(0) 0.272838 0.373949

(0)

M 0.924779 4.73020

(0)

N 1.19764 -0.200000

(1)

L 0.625701 0.0239035

M(1) 0.792014 1.24615

(1)

N 2.46022 -8.000000

The Twu alpha function is a theoretically-based function that is currently

recognized as the best available alpha function. It behaves better than other

functions at supercritical conditions (T > Tc).

determined from regression of pure-component vapor pressure data or other

data such as liquid heat capacity.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

PRTWUP/1 L — X — — —

PRTWUP/2 M 0 X — — —

PRTWUP/3 N 0 X — — —

This is an extension of the Peng-Robinson alpha function which provides a

more accurate fit of vapor pressure for polar compounds.

(7)

For c2,i = 0 and c3,i = 0, this expression reduces to the standard Peng-

Robinson formulation if c2,i = mi. You can use vapor pressure data if the

temperature is subcritical to regress the constants. If the temperature is

supercritical, c2,i and c3,i are set to 0.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

TCPR Tci TC X 5.0 2000.0 TEMPERATURE

PCPR pci PC X 105 108 PRESSURE

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

PRMCP/1 c1,i — X — — —

PRMCP/2 c2,i 0 X — — —

PRMCP/3 c3,i 0 X — — —

The Schwartzentruber-Renon-Watanasiri alpha function is:

(8)

Where mi is computed by equation 5. The polar parameters p1,i, p2,i and p3,i

are comparable with the c parameters of the Mathias-Copeman expression.

Equation 8 reduces to the standard Peng-Robinson formulation if the polar

parameters are zero. Equation 8 is used only for below-critical temperatures.

For above-critical temperatures, the Boston-Mathias extrapolation is used.

Use equation 6 with:

(9)

(10)

Name/Element Limit Limit

TCPR Tci TC X 5.0 2000.0 TEMPERATURE

5 8

PCPR pci PC X 10 10 PRESSURE

OMGPR ωi OMEGA X -0.5 2.0 —

PRSRP/1 — X — — —

PRSRP/2 0 X — — —

PRSRP/3 0 X — — —

The alpha functions in Peng-Robinson-based equation-of-state models is

provided in the following table. You can verify and change the value of

possible option codes on the Properties | Property Methods | Model form.

Alpha function Model name First Option code

Standard Peng Robinson ESPRSTD0, ESPRSTD 1

Standard PR/ ESPR0, ESPR 0

Boston-Mathias ESPRWS0, ESPRWS 0

ESPRV20, ESPRV2 0

Extended Gibbons- ESPR0, ESPR 2

Laughton

Twu Generalized alpha ESPR0, ESPR 3

function

Twu alpha function ESPR0, ESPR 4

Alpha function Model name First Option code

Mathias-Copeman ESPRWS0, ESPRWS 2

ESPRV20, ESPRV2 2

Schwartzentruber- ESPRWS0, ESPRWS 3 (default)

Renon- ESPRV20, ESPRV2 3 (default)

Watanasiri

References

J. F. Boston and P.M. Mathias, "Phase Equilibria in a Third-Generation Process

Simulator" in Proceedings of the 2nd International Conference on Phase

Equilibria and Fluid Properties in the Chemical Process Industries, West Berlin,

(17-21 March 1980) pp. 823-849.

D.-Y. Peng and D.B. Robinson, "A New Two-Constant Equation-of-state," Ind.

Eng. Chem. Fundam., Vol. 15, (1976), pp. 59-64.

P.M. Mathias and T.W. Copeman, "Extension of the Peng-Robinson Equation-

of-state To Complex Mixtures: Evaluation of the Various Forms of the Local

Composition Concept",Fluid Phase Eq., Vol. 13, (1983), p. 91.

J. Schwartzentruber, H. Renon, and S. Watanasiri, "K-values for Non-Ideal

Systems:An Easier Way," Chem. Eng., March 1990, pp. 118-124.

G. Soave, "Equilibrium Constants for a Modified Redlich-Kwong Equation-of-

state," Chem Eng. Sci., Vol. 27, (1972), pp. 1196-1203.

C.H. Twu, J. E. Coon, and J.R. Cunningham, "A New Cubic Equation of State,"

Fluid Phase Equilib., Vol. 75, (1992), pp. 65-79.

C.H. Twu, D. Bluck, J.R. Cunningham, and J.E. Coon, "A Cubic Equation of

State with a New Alpha Function and a New Mixing Rule," Fluid Phase Equilib.,

Vol. 69, (1991), pp. 33-50.

The pure component parameters for the Redlich-Kwong equation-of-state are

calculated as:

(1)

(2)

equation-of-state under these conditions:

(3)

Note: You can choose any of the alpha functions described here, but you

cannot define multiple property methods based on this model using different

alpha functions within the same run.

In the Redlich-Kwong equation-of-state, alpha is:

(4)

temperature units.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

TC Tci — — 5.0 2000.0 TEMPERATURE

PC pci — — 105 108 PRESSURE

Soave Modification

The parameter αi is a temperature function introduced by Soave in the

Redlich-Kwong equation-of-state to improve the correlation of the pure

component vapor pressure:

(5)

Equation 3 still holds. The parameter mi can be correlated with the acentric

factor:

(6)

formulation. The Soave alpha function is adequate for hydrocarbons and other

nonpolar compounds, but is not sufficiently accurate for polar compounds.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

TCRKS Tci TC X 5.0 2000.0 TEMPERATURE

5 8

PCRKS pci PC X 10 10 PRESSURE

OMGRKS ωi OMEGA X -0.5 2.0 —

Boston-Mathias Extrapolation

For light gases at high reduced temperatures (> 5), equation 5 gives

unrealistic results. The boundary conditions are that attraction between

molecules should vanish for extremely high temperatures, and reduces

asymptotically to zero. Boston and Mathias derived an alternative function for

temperatures higher than critical:

(7)

With

di =

ci =

Where:

mi = Computed by equation 6

Equation 5 = Used for subcritical temperatures

Additional parameters are not needed.

This is an extension of the Soave alpha function which provides a more

accurate fit of vapor pressure for polar compounds.

(8)

formulation, equations 5 and 6. For temperatures above critical, the Boston-

Mathias extrapolation is used, that is, equation 7 with:

(9)

(10)

is the basis for the RK-ASPEN property method. This alpha function is also

available as an option for SRK, SRKKD, SRK-ML, RK-SOAVE, and RKS-BM.

See Soave-Redlich-Kwong Option Codes for more information.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

TCRKA Tci TC X 5.0 2000.0 TEMPERATURE

5 8

PCRKA pci PC X 10 10 PRESSURE

OMGRKA ωi OMEGA X -0.5 2.0 —

† ηi — X -2.0 2.0 —

† RKAPOL for Redlich-Kwong-Aspen, SRKPOL for SRK and SRKKD, SRKMLP for

SRK-ML, RKSPOL for RKS-BM, or RKSSPO for RK-SOAVE.

An extension of the Mathias approach is:

(11)

Where mi is computed by equation 6. If the polar parameters p1,i, p2,i and p3,i

are zero, equation 11 reduces to the standard Redlich-Kwong-Soave

formulation. You can use vapor pressure data to regress the constants if the

temperature is subcritical. Equation 11 is used only for temperatures below

critical.

The Boston-Mathias extrapolation is used for temperatures above critical, that

is, with:

(12)

(13)

basis for the SR-POLAR property method.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

TCRKU Tci TC X 5.0 2000.0 TEMPERATURE

5 8

PCRKU pci PC X 10 10 PRESSURE

OMGRKU ωi OMEGA X -0.5 2.0 —

RKUPP0 p1,i — X — — —

RKUPP1 p2,i 0 X — — —

RKUPP2 p3,i 0 X — — —

The Mathias-Copeman alpha function is suitable for use with both polar and

nonpolar components. It has the flexibility to fit the vapor pressure of most

substances from the triple point to the critical point.

(14)

For c2,i=0 and c3,i=0 this expression reduces to the standard Redlich-Kwong-

Soave formulation if c1,i=mi. If the temperature is subcritical, use vapor

pressure data to regress the constants. If the temperature is supercritical, set

c2,i and c3,i to 0.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

TCRKS Tci TC X 5.0 2000.0 TEMPERATURE

5 8

PCRKS pci PC X 10 10 PRESSURE

RKSMCP/1 c1,i — X — — —

RKSMCP/2 c2,i 0 X — — —

RKSMCP/3 c3,i 0 X — — —

The Schwartzentruber-Renon-Watanasiri alpha function is:

(15)

Where mi is computed by equation 6 and the polar parameters p1,i, p2,i and p3,i

are comparable with the c parameters of the Mathias-Copeman expression.

Equation 15 reduces to the standard Redlich-Kwong-Soave formulation if the

polar parameters are zero. Equation 15 is very similar to the extended

Mathias equation, but it is easier to use in data regression. It is used only for

temperatures below critical. The Boston-Mathias extrapolation is used for

temperatures above critical, that is, use equation 7 with:

(16)

(17)

Name/Element Limit Limit

TCRKS Tci TC X 5.0 2000.0 TEMPERATURE

5 8

PCRKS pci PC X 10 10 PRESSURE

OMGRKS ωi OMEGA X -0.5 2.0 —

RKSSRP/1 p1,i — X — — —

RKSSRP/2 p2,i 0 X — — —

RKSSRP/3 p3,i 0 X — — —

The extended Gibbons-Laughton alpha function is suitable for use with both

polar and nonpolar components. It has the flexibility to fit the vapor pressure

of most substances from the triple point to the critical point.

parameters.

This function is equivalent to the standard Soave alpha function if

predicting negative alpha, when Tri>1 the Boston-Mathias alpha function is

used instead.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

RKSGLP/1 X — X — — —

RKSGLP/2 Y 0 X — — —

RKSGLP/3 Z 0 X — — —

RKSGLP/4 n 2 X — — —

RKSGLP/5 Tlower 0 X — — TEMPERATURE

RKSGLP/6 Tupper 1000 X — — TEMPERATURE

The Twu generalized alpha function is a theoretically-based function that is

currently recognized as the best available alpha function. It behaves better

than other functions at supercritical conditions (T > Tc) and when the acentric

factor is large. The improved behavior at high values of acentric factor is

important for high molecular weight pseudocomponents. There is no limit on

the minimum value of acentric factor that can be used with this function.

Where the L, M, and N are parameters that vary depending on the equation of

state and whether the temperature is above or below the critical temperature

of the component.

For Soave-Redlich-Kwong:

Subcritical T Supercritical T

L(0) 0.544000 0.379919

(0)

M 1.01309 5.67342

(0)

N 0.935995 -0.200000

(1)

L 0.544306 0.0319134

M(1) 0.802404 1.28756

(1)

N 3.10835 -8.000000

The use of alpha functions in Soave-Redlich-Kwong based equation-of-state

models is given in the following table. You can verify and change the value of

possible option codes on the Properties | Property Methods | Models

sheet.

Alpha Function Model Name First Option Code

original RK ESRK0, ESRK —

standard RKS ESRKSTD0, ESRKSTD —

* 1, 2 (default)

standard RKS/Boston-Mathias * 0

ESRKSWS0, ESRKSWS 1

ESRKSV10, ESRKV1 1

ESRKSV20, ESRKSV2 1

Mathias/Boston-Mathias ESRKA0, ESRKA —

Extended Mathias/Boston- ESRKU0, ESRKU —

Mathias

Mathias-Copeman ESRKSV10, ESRKSV1 2

ESRKSV20, ESRKSV2 2

Schwartzentruber-Renon- ESPRWS0, ESPRWS 3 (default)

Watanasiri ESRKSV10, ESRKSV1 3 (default)

ESRKSV20, ESRKSV2 3 (default)

Twu generalized * 5

Gibbons-Laughton with Patel * 3

extension

Mathias for T < Tc; Boston- * 4

Mathias for T > Tc

ESRKSML0. The default alpha function (option code 2) for these models is the

standard RKS alpha function, except that the Grabovsky-Daubert alpha

function is used for H2: α = 1.202 exp(-0.30228xTri)

References

J. F. Boston and P.M. Mathias, "Phase Equilibria in a Third-Generation Process

Simulator" in Proceedings of the 2nd International Conference on Phase

Equilibria and Fluid Properties in the Chemical Process Industries, West Berlin,

(17-21 March 1980), pp. 823-849.

P. M. Mathias, "A Versatile Phase Equilibrium Equation-of-state", Ind. Eng.

Chem. Process Des. Dev., Vol. 22, (1983), pp. 385–391.

P.M. Mathias and T.W. Copeman, "Extension of the Peng-Robinson Equation-

of-state To Complex Mixtures: Evaluation of the Various Forms of the Local

Composition Concept", Fluid Phase Eq., Vol. 13, (1983), p. 91.

O. Redlich and J. N. S. Kwong, "On the Thermodynamics of Solutions V. An

Equation-of-state. Fugacities of Gaseous Solutions," Chem. Rev., Vol. 44,

(1949), pp. 223–244.

J. Schwartzentruber and H. Renon, "Extension of UNIFAC to High Pressures

and Temperatures by the Use of a Cubic Equation-of-state," Ind. Eng. Chem.

Res., Vol. 28, (1989), pp. 1049–1055.

J. Schwartzentruber, H. Renon, and S. Watanasiri, "K-values for Non-Ideal

Systems:An Easier Way," Chem. Eng., March 1990, pp. 118-124.

G. Soave, "Equilibrium Constants for a Modified Redlich-Kwong Equation-of-

state," Chem Eng. Sci., Vol. 27, (1972), pp. 1196-1203.

C.H. Twu, W.D. Sim, and V. Tassone, "Getting a Handle on Advanced Cubic

Equations of State", Chemical Engineering Progress, Vol. 98 #11 (November

2002) pp. 58-65.

Huron and Vidal (1979) used a simple thermodynamic relationship to equate

the excess Gibbs energy to expressions for the fugacity coefficient as

computed by equations of state:

(1)

assumptions are made. If Equation 1 is evaluated at infinite pressure, the

mixture must be liquid-like and extremely dense. It can be assumed that:

(2)

(3)

contains the excess Gibbs energy at an infinite pressure:

(4)

Where:

(5)

cubic equation-of-state can be written as:

(6)

equations of state are:

Equation-of-state λ1 λ2

Peng-Robinson

Redlich-Kwong-Soave 1 0

This expression can be used at any pressure as a mixing rule for the

parameter. The mixing rule for b is fixed by equation 3. Even when used at

other pressures, this expression contains the excess Gibbs energy at infinite

pressure. You can use any activity coeffecient model to evaluate the excess

Gibbs energy at infinite pressure. Binary interaction coefficients must be

regressed. The mixing rule used contains as many binary parameters as the

activity coefficient model chosen.

This mixing rule has been used successfully for polar mixtures at high

pressures, such as systems containing light gases. In theory, any activity

coefficient model can be used. But the NRTL equation (as modified by Huron

and Vidal) has demonstrated better performance.

The Huron-Vidal mixing rules combine extreme flexibility with thermodynamic

consistency, unlike many other mole-fraction-dependent equation-of-state

mixing rules. The Huron-Vidal mixing rules do not allow flexibility in the

description of the excess molar volume, but always predict reasonable excess

volumes.

The Huron-Vidal mixing rules are theoretically incorrect for low pressure,

because quadratic mole fraction dependence of the second virial coefficient (if

derived from the equation-of-state) is not preserved. Since equations of state

are primarily used at high pressure, the practical consequences of this

drawback are minimal.

The Gibbs energy at infinite pressure and the Gibbs energy at an arbitrary

high pressure are similar. But the correspondence is not close enough to

make the mixing rule predictive.

There are several methods for modifying the Huron-Vidal mixing rule to make

it more predictive. The following three methods are used in Aspen Physical

Property System equation-of-state models:

• The modified Huron-Vidal mixing rule, second order approximation

(MHV2)

• The Predictive SRK Method (PSRK)

• The Wong-Sandler modified Huron-Vidal mixing rule (WS)

These mixing rules are discussed separately in the following sections. They

have major advantages over other composition-dependent equation-of-state

mixing rules.

References

M.- J. Huron and J. Vidal, "New Mixing Rules in Simple Equations of State for

representing Vapour-liquid equilibria of strongly non-ideal mixtures," Fluid

Phase Eq., Vol. 3, (1979), pp. 255-271.

Dahl and Michelsen (1990) use a thermodynamic relationship between excess

Gibbs energy and the fugacity computed by equations of state. This

relationship is equivalent to the one used by Huron and Vidal:

(1)

The advantage is that the expressions for mixture and pure component

fugacities do not contain the pressure. They are functions of compacity V/b

and α:

(2)

Where:

(3)

and

(4)

With:

(5)

The constants λ1 and λ2, which depend only on the equation-of-state (see

Huron-Vidal Mixing Rules) occur in equations 2 and 4.

Instead of using infinite pressure for simplification of equation 1, the condition

of zero pressure is used. At p = 0 an exact relationship between the

compacity and α can be derived. By substitution the simplified equation q(α)

is obtained, and equation 1 becomes:

(6)

approximation is possible below that threshold. Dahl and Michelsen use a

second order polynomial fitted to the analytical solution for 10 < α < 13 that

can be extrapolated to low alpha:

(7)

combination of equations 6 and 7 form the MHV2 mixing rule. Excess Gibbs

energies, from any activity coefficient model with parameters optimized at

low pressures, can be used to determine α, if αi, bi, and b are known. To

compute b, a linear mixing rule is assumed as in the original Huron-Vidal

mixing rules:

(8)

The MHV2 mixing rule was the first successful predictive mixing rule for

equations of state. This mixing rule uses previously determined activity

coefficient parameters for predictions at high pressures. UNIFAC was chosen

as a default for its predictive character. The Lyngby modified UNIFAC

formulation was chosen for optimum performance (see UNIFAC (Lyngby

Modified)). However, any activity coefficient model can be used when its

binary interaction parameters are known.

Like the Huron-Vidal mixing rules, the MHV2 mixing rules are not flexible in

the description of the excess molar volume. The MHV2 mixing rules are

theoretically incorrect at the low pressure limit. But the practical

consequences of this drawback are minimal (see Huron-Vidal Mixing Rules,

this chapter).

Reference: S. Dahl and M.L. Michelsen, "High-Pressure Vapor-Liquid

Equilibrium with a UNIFAC-based Equation-of-state," AIChE J., Vol. 36,

(1990), pp. 1829-1836.

Predictive Soave-Redlich-Kwong-Gmehling

Mixing Rules

These mixing rules by Holderbaum and Gmehling (1991) use a relationship

between the excess Helmholtz energy and equation-of-state. They do not use

a relationship between equation-of-state properties and excess Gibbs energy,

as in the Huron-Vidal mixing rules. The pressure-explicit expression for the

equation-of-state is substituted in the thermodynamic equation:

(1)

(2)

Where both Ai* and Am are calculated by using equation 1. Ai* and Am are

written in terms of equation-of-state parameters.

The simplification of constant packing fraction (Vm / b) is used:

(3)

With:

(4)

Therefore:

(5)

(6)

Where Λ' is slightly different from Λ for the Huron-Vidal mixing rule:

(7)

Rules). If equation 6 is applied at infinite pressure, the packing fraction goes

to 1. The excess Helmholtz energy is equal to the excess Gibbs energy. The

Huron-Vidal mixing rules are recovered.

The goal of these mixing rules is to be able to use binary interaction

parameters for activity coefficient models at any pressure. These parameters

have been optimized at low pressures. UNIFAC is chosen for its predictive

character. Two issues exist: the packing fraction is not equal to one, and the

excess Gibbs and Helmholtz energy are not equal at the low pressure where

the UNIFAC parameters have been derived.

Fischer (1993) determined that boiling point, the average packing fraction for

about 80 different liquids with different chemical natures was 1.1. Adopting

this value, the difference between liquid excess Gibbs energy and liquid

excess Helmholtz energy can be computed as:

(8)

The result is a predictive mixing rule for cubic equations of state. But the

original UNIFAC formulation gives the best performance for any binary pair

with interactions available from UNIFAC. Gas-solvent interactions are

unavailable.

At the University of Oldenburg in Germany, the UNIFAC groups were

extended with often-occurring gases. New group interactions were

determined from gas-solvent data, specific to the Redlich-Kwong-Soave

equation-of-state. The new built-in parameters to the Aspen Physical Property

System are activated when using the PSRK equation-of-state model.

The PSRK method has a lot in common with the Huron-Vidal mixing rules. The

mole fraction is dependent on the second virial coefficient and excess volume

is predicted. These are minor disadvantages.

References

K. Fischer, "Die PSRK-Methode: Eine Zustandsgleichung unter Verwendung

des UNIFAC-Gruppenbeitragsmodells," (Düsseldorf: VDI Fortschrittberichte,

Reihe 3: Verfahrenstechnik, Nr. 324, VDI Verlag GmbH, 1993).

T. Holderbaum and J. Gmehling, "PSRK: A Group Contribution Equation-of-

state based on UNIFAC," Fluid Phase Eq., Vol. 70, (1991), pp. 251-265.

These mixing rules use a relationship between the excess Helmholtz energy

and equation-of-state. They do not use a relationship between equation-of-

state properties and excess Gibbs energy, as in the Huron-Vidal mixing rules.

The pressure-explicit expression for the equation-of-state is substituted in the

thermodynamic equation:

(1)

(2)

Where both Ai* and Am are calculated by using equation 1. Ai* and Am are

written in terms of equation-of-state parameters.

Like Huron and Vidal, the limiting case of infinite pressure is used. This

simplifies the expressions for Ai* and Am. Equation 2 becomes:

(3)

Equation 3 is completely analogous to the Huron-Vidal mixing rule for the

excess Gibbs energy at infinite pressure. (See equation 4, Huron-Vidal Mixing

Rules.) The excess Helmholtz energy can be approximated by the excess

Gibbs energy at low pressure from any liquid activity coefficient model. Using

the Helmholtz energy permits another mixing rule for b than the linear mixing

rule. The mixing rule for b is derived as follows. The second virial coefficient

must depend quadratically on the mole fraction:

(4)

With:

(5)

The relationship between the equation-of-state at low pressure and the virial

coefficient is:

(6)

(7)

Wong and Sandler discovered the following mixing rule to satisfy equation 4

(using equations 6 and 7):

approximated by the Gibbs energy at low pressure. The difference between

the two functions is corrected by fitting kij until the excess Gibbs energy from

the equation-of-state (using the mixing rules 3 and 8) is equal to the excess

Gibbs energy computed by an activity coeffecient model. This is done at a

specific mole fraction and temperature.

This mixing rule accurately predicts the VLE of polar mixtures at high

pressures. UNIFAC or other activity coeffecient models and parameters from

the literature are used. Gas solubilities are not predicted. They must be

regressed from experimental data.

Unlike other (modified) Huron-Vidal mixing rules, the Wong and Sandler

mixing rule meets the theoretical limit at low pressure. The use of kij does

influence excess molar volume behavior. For calculations where densities are

important, check whether they are realistic.

References

D. S. Wong and S. I. Sandler, "A Theoretically Correct New Mixing Rule for

Cubic Equations of State for Both Highly and Slightly Non-ideal Mixtures,"

AIChE J., Vol. 38, (1992), pp. 671 – 680.

D. S. Wong, H. Orbey, and S. I. Sandler, "Equation-of-state Mixing Rule for

Non-ideal Mixtures Using Available Activity Coefficient Model Parameters and

That Allows Extrapolation over Large Ranges of Temperature and Pressure",

Ind Eng Chem. Res., Vol. 31, (1992), pp. 2033 – 2039.

H. Orbey, S. I. Sandler and D. S. Wong, "Accurate Equation-of-state

Predictions at High Temperatures and Pressures Using the Existing UNIFAC

Model," Fluid Phase Eq., Vol. 85, (1993), pp. 41 – 54.

The Aspen Physical Property System has the following built-in activity

coefficient models. This section describes the activity coefficient models

available.

Model Type

Bromley-Pitzer Electrolyte

Chien-Null Regular solution, local composition

Constant Activity Coefficient Arithmetic

COSMO-SAC Regular solution

Electrolyte NRTL Electrolyte

ENRTL-SAC Segment contribution, electrolyte

Hansen Regular solution

Ideal Liquid Ideal

NRTL (Non-Random-Two-Liquid) Local composition

NRTL-SAC Segment contribution

Pitzer Electrolyte

Polynomial Activity Coefficient Arithmetic

Redlich-Kister Arithmetic

Scatchard-Hildebrand Regular solution

Three-Suffix Margules Arithmetic

UNIFAC Group contribution

UNIFAC (Lyngby modified) Group contribution

UNIFAC (Dortmund modified) Group contribution

UNIQUAC Local composition

Van Laar Regular solution

Wagner interaction parameter Arithmetic

Wilson Local composition

Wilson with Liquid Molar Volume Local composition

The Bromley-Pitzer activity coefficient model is a simplified Pitzer activity

coefficient model with Bromley correlations for the interaction parameters.

See Working Equations for a detailed description. This model has predictive

capabilities. It can be used to compute activity coefficients for aqueous

electrolytes up to 6 molal ionic strength, but is less accurate than the Pitzer

model if the parameter correlations are used. The model should not be used

for mixed-solvent electrolyte systems.

The Bromley-Pitzer model in the Aspen Physical Property System involves

user-supplied parameters, used in the calculation of binary parameters for the

electrolyte system.

Parameters β(0), β(1), β(2), β(3), and θ have five elements to account for

temperature dependencies. Elements P1 through P5 follow the temperature

dependency relation:

Where:

Tref = 298.15K

The user must:

• Supply these elements using a Properties Parameters Binary T-Dependent

form.

• Specify Comp ID i and Comp ID j on this form, using the same order that

appears on the Components Specifications Selection sheet form.

Parameter Name Symbol No. of Elements Default Units

Ionic Unary Parameters

GMBPB βion 1 0 —

GMBPD δion 1 0 —

Cation-Anion Parameters

GMBPB0 β(0) 5 0 —

GMBPB1 β(1) 5 0 —

GMBPB2 β(2) 5 0 —

GMBPB3 β(3) 5 0 —

Cation-Cation Parameters

GMBPTH θcc' 5 0 —

Anion-Anion Parameters

GMBPTH θaa' 5 0 —

Molecule-Ion and Molecule-Molecule Parameters

GMBPB0 β(0) 5 0 —

GMBPB1 β(1) 5 0 —

Working Equations

The complete Pitzer equation (Fürst and Renon, 1982) for the excess Gibbs

energy is (see also equation 4):

(1)

Where:

GE = Excess Gibbs energy

R = Gas constant

T = Temperature

nw = Kilograms of water

zi = Charge number of ion i

= molality of ion i

Where:

xi = Mole fraction of ion i

xw = Mole fraction of water

Mw = Molecular weight of water (g/mol)

ni = Moles of ion i

a function of ionic strength; these terms are discussed in Pitzer Activity

Coefficient Model, which has a detailed discussion of the Pitzer model.

The C term and the Ψ term are dropped from equation 1 to give the

simplified Pitzer equation.

(2)

Where:

Bij = f(βij(0),βij(1),βij(2),βij(3))

Therefore, the simplified Pitzer equation has two types of binary interaction

parameters, β 's and θ''s. There are no ternary interaction parameters with

the simplified Pitzer equation.

Note that the Pitzer model parameter databank described in Physical Property

Data, Chapter 1, is not applicable to the simplified Pitzer equation.

A built-in empirical correlation estimates the β(0) and β(1) parameters for

cation-anion pairs from the Bromley ionic parameters, βion and δion (Bromley,

1973). The estimated values of β(0)'s and β(1)'s are overridden by the user's

input. For parameter naming and requirements, see Bromley-Pitzer Activity

Coefficient Model.

References

L.A. Bromley, "Thermodynamic Properties of Strong Electrolytes in Aqueous

Solution, " AIChE J., Vol. 19, No. 2, (1973), pp. 313 – 320.

W. Fürst and H. Renon, "Effects of the Various Parameters in the Application

of Pitzer's Model to Solid-Liquid Equilibrium. Preliminary Study for Strong 1-1

Electrolytes," Ind. Eng. Chem. Process Des. Dev., Vol. 21, No. 3, (1982),

pp. 396-400.

Parameter Conversion

For n-m electrolytes, n and m>1 (2-2, 2-3, 3-4, and so on), the parameter

β(3) corresponds to Pitzer's β(1); β(2) is the same in both Aspen Physical

Property System and original Pitzer models. Pitzer refers to the n-m

electrolyte parameters as β(1), β(2), β(0). β(0) and β(2) retain their meanings in

both models, but Pitzer's β(1) is Aspen Physical Property System β(3). Be

careful to make this distinction when entering n-m electrolyte parameters.

Chien-Null

The Chien-Null model calculates liquid activity coefficients and it can be used

for highly non-ideal systems. The generalized expression used in its derivation

can be adapted to represent other well known formalisms for the activity

coefficient by properly defining its binary terms. This characteristic allows the

model the use of already available binary parameters regressed for those

other liquid activity models with thermodynamic consistency.

The equation for the Chien-Null liquid activity coeficient is:

Where:

Rji = Aji / Aij

Aii = 0

Subscripts i and j are component indices.

The choice of model and parameters can be set for each binary pair

constituting the process mixture by assigning the appropriate value to the

ICHNUL parameter.

The Regular Solution and Scatchard-Hamer models are regained by

substituting in the general expression (ICHNUL = 1 or 2).

Vji = Sji = Vj*,l / Vi*,l

Where:

Vj*,l = Liquid molar volume of component i

The Chien-Null activity coefficient model collapses to the Margules liquid

activity coefficient expression by setting (ICHNUL = 3):

Vji = Sji = 1

The Van Laar Liquid activity coefficient model is obtained when the V and S

parameters in the Chien-Null models are set to the ratio of the cross terms of

A (ICHNUL = 4:)

Vji = Sji = Aji / Aij

Finally, the Renon or NRTL model is obtained when we make the following

susbstitutions in the Chien-Null expression for the liquid activity (ICHNUL =

5).

Sji = RjiAji / Aij

Aji = 2τjiGji

Vji = Gji

The following are defined for the Non-Random Two-Liquid activity coefficient

model, where:

Cij = cij + dij (T - 273.15 K)

cji = cij

dji = dij

The binary parameters CHNULL/1, CHNULL/2, and CHNULL/3 can be

determined from regression of VLE and/or LLE data. Also, if you have

parameters for many of the mixture pairs for the Margules, Van Laar,

Scatchard-Hildebrand, and NRTL (Non-Random-Two-Liquid) activity models,

you can use them directly with the Chien-Null activity model after selecting

the proper code (ICHNUL) to identify the source model and entering the

appropriate activity model parameters.

Parameter Symbol Default Lower Upper Units

Name/Element Limit Limit

ICHNUL — 3 1 6 —

CHNULL/1 aij 0 — — —

CHNULL/2 bij 0 — — —

CHNULL/3 Vij 0 — — —

available for each binary pair of interest. The following values are allowed for

ICHNUL:

ICHNUL = 1 or 2, sets the model to the Scatchard-Hamer or regular solution

model for the associated binary;

ICHNUL = 3, sets the model to the Three-Suffix Margules activity model for

the associated binary;

ICHNUL = 4, sets the model to the Van Laar formalism for the activity model

for the associated binary;

ICHNUL = 5, sets the model to the NRTL (Renon) formalism for the activity

model for the associated binary.

ICHNUL = 6, sets the model to the full Chien-Null formalism for the activity

model for the associated binary.

When you specify a value for the ICHNUL parameter that is different than the

default, you must enter the appropriate binary model parameters for the

chosen activity model directly. The routine will automatically convert the

expressions and parameters to conform to the Chien-Null formulation.

This approach is used exclusively in metallurgical applications where multiple

liquid and solid phases can coexist. You can assign any value to the activity

coefficient of component i. Use the Properties Parameters Unary Scalar form.

The equation is:

γi = ai

Parameter Symbol Default MDS Upper Lower Units

Name/Element Limit Limit

GMCONS ai 1.0 x — — —

COSMO-SAC

Cosmo-SAC is a solvation model that describes the electric fields on the

molecular surface of species that are polarizable. It requires a fairly

complicated quantum mechanical calculation, but this calculation must be

done only once for a particular molecule; then the results can be stored. In its

final form, it uses individual atoms as the building blocks for predicting phase

equilibria instead of functional groups. This model formulation provides a

considerably larger range of applicability than group-contribution methods.

The calculation for liquid nonideality is only slightly more computationally

intensive than activity-coefficient models such as NRTL or UNIQUAC. Cosmo-

SAC complements the UNIFAC group-contribution method, because it is

applicable to virtually any mixture.

The Cosmo-SAC model calculates liquid activity coefficients. The equation for

the Cosmo-SAC model is:

With

Where:

contribution to γi

component i

ΓS(σm) = Segment activity coefficient of segment σm in

solvent mixture

ΔWHB(σm,σn) = Hydrogen-bonding contribution to exchange energy

between segments σm and σn

z = Coordination number, 10

Vi = Molecular volume of component i

Ai = Molecular surface area of component i

aeff = Standard segment surface area, 7.50 Å2

Veff = Standard component volume, 66.69 Å3

Aeff = Standard component surface area, 79.53 Å2

The Cosmo-SAC model does not require binary parameters. For each

component, it has six input parameters. CSACVL is the component volume

parameter which is always defined in cubic angstroms, regardless of chosen

units sets. SGPRF1 to SGPRF5 are five component sigma profile parameters;

each can store up to 12 points of sigma profile values. All six input

parameters are obtained from COSMO calculation. The Aspen Physical

Property System includes a database of sigma profiles for over 1400

compounds from Mullins et al. (2006). The parameters were obtained by

permission from the Virginia Tech Sigma Profile Database website

(http://www.design.che.vt.edu/VT-2004.htm). Aspen Technology, Inc. does

not claim proprietary rights to these parameters.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

CSACVL Vi — x — — VOLUME (Å3)

SGPRF1 Ai pi(1-12) — x — — —

SGPRF2 Ai pi(13-24) — x — — —

SGPRF3 Ai pi(25-36) — x — — —

SGPRF4 Ai pi(37-48) — x — — —

SGPRF5 Ai pi(49-51) — x — — —

Option Codes

The primary version of COSMO-SAC is the model by Lin and Sandler (2002).

Two other versions are available using an option code, as detailed in the table

below:

Option Description

Code

1 COSMO-SAC model by Lin and Sandler (2002)

2 COSMO-RS model by Klamt (1995)

3 Lin and Sandler model with modified exchange energy (Lin

et al., 2002)

References

A. Klamt, "Conductor-like Screening Model for Real Solvents: A New Approach

to the Quantitative Calculation of Solvation Phenomena," J. Phys. Chem. 99,

2224 (1995).

S.-T. Lin, P. M. Mathias, Y. Song, C.-C. Chen, and S. I. Sandler,

"Improvements of Phase-Equilibrium Predictions for Hydrogen-Bonding

Systems from a New Expression for COSMO Solvation Models," presented at

the AIChE Annual Meeting, Indianapolis, IN, 3-8 November (2002).

S.-T. Lin and S. I. Sandler, "A Priori Phase Equilibrium Prediction from a

Segment Contribution Solvation Model," Ind. Eng. Chem. Res. 41, 899

(2002).

E. Mullins, et al. "Sigma-Profile Database for Using COSMO-Based

Thermodynamic Methods," Ind. Eng. Chem. Res. 45, 4389 (2006).

The Electrolyte Non-Random Two Liquid (NRTL) model is a versatile model for

the calculation of activity coefficients. Using binary and pair parameters, the

model can represent aqueous electrolyte systems as well as mixed solvent

electrolyte systems over the entire range of electrolyte concentrations. This

model can calculate activity coefficients for ionic species and molecular

species in aqueous electrolyte systems as well as in mixed solvent electrolyte

systems. The model reduces to the well-known NRTL model when electrolyte

concentrations become zero (Renon and Prausnitz, 1969).

The electrolyte NRTL model uses the infinite dilution aqueous solution as the

reference state for ions. It adopts the Born equation to account for the

transformation of the reference state of ions from the infinite dilution mixed

solvent solution to the infinite dilution aqueous solution.

Water must be present in the electrolyte system in order to compute the

transformation of the reference state of ions. Thus, it is necessary to

introduce a trace amount of water to use the model for nonaqueous

electrolyte systems.

The Aspen Physical Property System uses the electrolyte NRTL model to

calculate activity coefficients, enthalpies, and Gibbs energies for electrolyte

systems. Model development and working equations are provided in

Theoretical Basis and Working Equations.

The adjustable parameters for the electrolyte NRTL model include the:

• Pure component dielectric constant coefficient of nonaqueous solvents

• Born radius of ionic species

• NRTL parameters for molecule-molecule, molecule-electrolyte, and

electrolyte-electrolyte pairs

The pure component dielectric constant coefficients of nonaqueous solvents

and Born radius of ionic species are required only for mixed-solvent

electrolyte systems. The temperature dependency of the dielectric constant of

solvent B is:

factor, α, and energy parameters, τ. The temperature dependency relations

of the electrolyte NRTL parameters are:

• Molecule-Molecule Binary Parameters:

For the electrolyte-electrolyte pair parameters, the two electrolytes must

share either one common cation or one common anion:

Where:

Tref = 298.15K

Many parameter pairs are included in the electrolyte NRTL model parameter

databank (see Physical Property Data, Chapter 1).

Option codes can affect the performance of this model. See Option Codes for

Activity Coefficient Models for details.

Parameter Symbol No. of Default MDS Units

Name Elements

Dielectric Constant Unary Parameters

CPDIEC AB 1 — — —

BB 1 0 — —

CB 1 298.15 — TEMPERATURE†

Parameter Symbol No. of Default MDS Units

Name Elements

Ionic Born Radius Unary Parameters

RADIUS ri 1 3x10-10 — LENGTH

Molecule-Molecule Binary Parameters

NRTL/1 ABB' — 0 x —

AB'B — 0 x —

NRTL/2 BBB' — 0 x TEMPERATURE†

BB'B — 0 x TEMPERATURE†

NRTL/3 αBB' = αB'B — .3 x —

NRTL/4 — — 0 x TEMPERATURE

NRTL/5 FBB' — 0 x TEMPERATURE

FB'B — 0 x TEMPERATURE

NRTL/6 GBB' — 0 x TEMPERATURE

GB'B — 0 x TEMPERATURE

Electrolyte-Molecule Pair Parameters

GMELCC Cca,B 1 0 x —

CB,ca 1 0 x —

GMELCD Dca,B 1 0 x TEMPERATURE†

DB,ca 1 0 x TEMPERATURE†

GMELCE Eca,B 1 0 x —

EB,ca 1 0 x —

GMELCN αca,B = αB,ca 1 .2 x —

Electrolyte-Electrolyte Pair Parameters

GMELCC Cca',ca'' 1 0 x —

Cca'',ca' 1 0 x —

Cc'a,c''a 1 0 x —

Cc''a,c'a 1 0 x —

†

GMELCD Dca',ca'' 1 0 x TEMPERATURE

†

Dca'',ca' 1 0 x TEMPERATURE

Dc'a,c''a 1 0 x TEMPERATURE†

Dc''a,c'a 1 0 x TEMPERATURE†

GMELCE Eca',ca'' 1 0 x —

Eca'',ca' 1 0 x —

Ec'a,c''a 1 0 x —

Ec''a,c'a 1 0 x —

GMELCN αca',ca'' = αca'',ca' 1 .2 x —

αc'a,c''a = αc''a,c'a 1 .2 x —

†

Certain Electrolyte NRTL activity coefficient model parameters are used with

reciprocal temperature terms:

• CPDIEC

• NRTL/2

• GMELCD for electrolyte-electrolyte or electrolyte-molecule pairs

When any of these parameters is specified, absolute temperature units are

used for the calculations in this model.

Reference: H. Renon, and J.M. Prausnitz, "Local Compositions in

Thermodynamic Excess Functions for Liquid Mixtures", AIChE J., Vol. 14, No.

1, (1968), pp. 135-144.

In this section, the theoretical basis of the model is explained and the working

equations are given. The different ways parameters can be obtained are

discussed with references to the databank directories and the Data

Regression System (DRS). The parameter requirements of the model are

given in Electrolyte NRTL Activity Coefficient Model.

The Electrolyte NRTL model was originally proposed by Chen et al., for

aqueous electrolyte systems. It was later extended to mixed solvent

electrolyte systems (Mock et al., 1984, 1986). The model is based on two

fundamental assumptions:

• The like-ion repulsion assumption: states that the local composition of

cations around cations is zero (and likewise for anions around anions).

This is based on the assumption that the repulsive forces between ions of

like charge are extremely large. This assumption may be justified on the

basis that repulsive forces between ions of the same sign are very strong

for neighboring species. For example, in salt crystal lattices the immediate

neighbors of any central ion are always ions of opposite charge.

• The local electroneutrality assumption: states that the distribution of

cations and anions around a central molecular species is such that the net

local ionic charge is zero. Local electroneutrality has been observed for

interstitial molecules in salt crystals.

Chen proposed an excess Gibbs energy expression which contains two

contributions: one contribution for the long-range ion-ion interactions that

exist beyond the immediate neighborhood of a central ionic species, and the

other related to the local interactions that exist at the immediate

neighborhood of any central species.

The unsymmetric Pitzer-Debye-Hückel model and the Born equation are used

to represent the contribution of the long-range ion-ion interactions, and the

Non-Random Two Liquid (NRTL) theory is used to represent the local

interactions. The local interaction contribution model is developed as a

symmetric model, based on reference states of pure solvent and pure

completely dissociated liquid electrolyte. The model is then normalized by

infinite dilution activity coefficients in order to obtain an unsymmetric model.

This NRTL expression for the local interactions, the Pitzer-Debye-Hückel

expression, and the Born equation are added to give equation 1 for the

excess Gibbs energy (see the following note).

(1)

This leads to

(2)

accepted in electrolyte thermodynamics and will be maintained here. The

reader should be warned not to confuse it with the meaning of * in classical

thermodynamics according to IUPAC/ISO, referring to a pure component

property. In fact in the context of G or γ, the asterisk as superscript is never

used to denote pure component property, so the risk of confusion is minimal.

For details on notation, see Chapter 1 of Physical Property Methods.

References

C.-C. Chen, H.I. Britt, J.F. Boston, and L.B. Evans, "Local Compositions Model

for Excess Gibbs Energy of Electrolyte Systems: Part I: Single Solvent, Single

Completely Dissociated Electrolyte Systems:, AIChE J., Vol. 28, No. 4, (1982),

p. 588-596.

C.-C. Chen, and L.B. Evans, "A Local Composition Model for the Excess Gibbs

Energy of Aqueous Electrolyte Systems," AIChE J., Vol. 32, No. 3, (1986), p.

444-459.

B. Mock, L.B. Evans, and C.-C. Chen, "Phase Equilibria in Multiple-Solvent

Electrolyte Systems: A New Thermodynamic Model," Proceedings of the 1984

Summer Computer Simulation Conference, p. 558.

B. Mock, L.B. Evans, and C.-C. Chen, "Thermodynamic Representation of

Phase Equilibria of Mixed-Solvent Electrolyte Systems," AIChE J., Vol. 32, No.

10, (1986), p. 1655-1664.

The Pitzer-Debye-Hückel formula, normalized to mole fractions of unity for

solvent and zero for electrolytes, is used to represent the long-range

interaction contribution.

(3)

with

(4)

(5)

Where:

xi = Mole fraction of component i

Ms = Molecular weight of the solvent

Aϕ = Debye-Hückel parameter

NA = Avogadro's number

ds = Mass density of solvent

Qe = Electron charge

T = Temperature

k = Boltzmann constant

Ix = Ionic strength (mole fraction scale)

xi = Mole fraction of component i

zi = Charge number of ion i

coefficient can then be derived.

(6)

The Born equation is used to account for the Gibbs energy of transfer of ionic

species from the infinite dilution state in a mixed-solvent to the infinite

dilution state in aqueous phase.

(7)

Where:

The expression for the activity coefficient can be derived from (7):

(8)

The Debye-Hückel theory is based on the infinite dilution reference state for

ionic species in the actual solvent media. For systems with water as the only

solvent, the reference state is the infinite dilution aqueous solution. For

mixed-solvent systems, the reference state for which the Debye-Hückel

theory remains valid is the infinite dilution solution with the corresponding

mixed-solvent composition. However, the molecular weight Ms, the mass

density ds, and the dielectric constant εs for the single solvent need to be

extended for mixed solvents; simple composition average mixing rules are

adequate to calculate them as follows:

(6a)

(7a)

(8a)

(8b)

(8c)

(8d)

Where:

xm = Mole fraction of the solvent m in the solution

Mm = Molecular weight of the solvent m

Vml = Molar volume of the solvent mixture

xnws = Sum of the mole fractions of all non-water

solvents.

Vnwsl = Liquid molar volume for the mixture of all non-

water solvents. It is calculated using the

Rackett equation.

It should be understood that equations 6a-8a should be used only in

equations 3, 4, and 7. Ms, ds, and εs were already assumed as constants when

deriving equations 6 and 8 for mixed-solvent systems.

The local interaction contribution is accounted for by the Non-Random Two

Liquid theory. The basic assumption of the NRTL model is that the nonideal

entropy of mixing is negligible compared to the heat of mixing: this is indeed

the case for electrolyte systems. This model was adopted because of its

algebraic simplicity and its applicability to mixtures that exhibit liquid phase

splitting. The model does not require specific volume or area data.

The effective local mole fractions Xji and Xii of species j and i, respectively, in

the neighborhood of i are related by:

(9)

Where:

Xj = xjCj

(Cj = zj for ions and Cj = unity for molecules)

Gji =

τji =

gji and gii are energies of interaction between species j and i, and i and i,

respectively. Both gij and αij are inherently symmetric (gij = gji and αij = αji).

Similarly,

(10)

Where:

Gji,ki =

τji,ki =

The derivations that follow are based on a simple system of one completely

dissociated liquid electrolyte ca and one solvent B. They will be later extended

to multicomponent systems. In this simple system, three different

arrangements exist:

In the case of a central solvent molecule with other solvent molecules,

cations, and anions in its immediate neighborhood, the principle of local

electroneutrality is followed: the surrounding cations and anions are such that

the neighborhood of the solvent is electrically neutral. In the case of a central

cation (anion) with solvent molecules and anions (cations) in its immediate

neighborhood, the principle of like-ion repulsion is followed: no ions of like

charge exist anywhere near each other, whereas opposite charged ions are

very close to each other.

The effective local mole fractions are related by the following expressions:

(11)

(central solvent cells)

(12)

(central cation cells)

(13)

(central anion cells)

Using equation 11 through 13 and the notation introduced in equations 9 and

10 above, expressions for the effective local mole fractions in terms of the

overall mole fractions can be derived.

(14)

i = c, a, or B

(15)

(16)

To obtain an expression for the excess Gibbs energy, let the residual Gibbs

energies, per mole of cells of central cation, anion, or solvent, respectively, be

, , and . These are then related to the

effective local mole fractions:

(17)

(18)

(19)

completely dissociated liquid electrolyte and of pure solvent. The reference

Gibbs energies per mole are then:

(20)

(21)

(22)

Where:

zc = Charge number on cations

za = Charge number on anions

The molar excess Gibbs energy can be found by summing all changes in

residual Gibbs energy per mole that result when the electrolyte and solvent in

their reference state are mixed to form the existing electrolyte system. The

expression is:

(23)

Using the previous relation for the excess Gibbs energy and the expressions

for the residual and reference Gibbs energy (equations 17 to 19 and 20 to

22), the following expression for the excess Gibbs energy is obtained:

(24)

molecules may be stated as:

(25)

Combining this expression with the expression for the effective local mole

fractions given in equations 9 and 10, the following equality is obtained:

(26)

(27)

(28)

and,

(29)

(30)

(31)

The binary parameters αca,B , τca,B and τB,ca are now the adjustable parameters

for an apparent binary system of a single electrolyte and a single solvent.

The excess Gibbs energy expression (equation 24) must now be normalized

to the infinite dilution reference state for ions:

(32)

(33)

activity coefficients of all three species can be determined.

(34)

(35)

(36)

Multicomponent Systems

The Electrolyte NRTL model can be extended to handle multicomponent

systems.

The excess Gibbs energy expression is:

(37)

Where:

j and k can be any species (a, C, or B)

The activity coefficient equation for molecular components is given by:

(38)

(39)

(40)

Where:

(41)

(42)

(43)

(44)

(45)

(46)

(47)

(48)

equation 37 when deriving the activity coefficients given by equations 38-40.

Parameters

The model adjustable parameters include:

• Pure component dielectric constant coefficient of nonaqueous solvents

• Born radius of ionic species

• NRTL interaction parameters for molecule-molecule, molecule-electrolyte,

and electrolyte-electrolyte pairs

Note that for the electrolyte-electrolyte pair parameters, the two electrolytes

must share either one common cation or one common anion.

Each type of the electrolyte NRTL parameter consists of both the

nonrandomness factor, α, and energy parameters, τ.

The pure component dielectric constant coefficients of nonaqueous solvents

and Born radius of ionic species are required only for mixed-solvent

electrolyte systems.

The temperature dependency relations of these parameters are given in

Electrolyte NRTL Activity Coefficient Model.

Heat of mixing is calculated from temperature derivatives of activity

coefficients. Heat capacity is calculated from secondary temperature

derivative of the activity coefficient. As a result, the temperature dependent

parameters are critical for modeling enthalpy correctly. It is recommended

that enthalpy data and heat capacity data be used to obtain these

temperature dependency parameters. See also Electrolyte NRTL Enthalpy and

Electrolyte NRTL Gibbs Energy.

Obtaining Parameters

In the absence of electrolytes, the electrolyte NRTL model reduces to the

NRTL equation which is widely used for non-electrolyte systems. Therefore,

molecule-molecule binary parameters can be obtained from binary

nonelectrolyte systems.

Electrolyte-molecule pair parameters can be obtained from data regression of

apparent single electrolyte systems.

Electrolyte-electrolyte pair parameters are required only for mixed

electrolytes with a common ion. Electrolyte-electrolyte pair parameters can

affect trace ionic activity precipitation. Electrolyte-electrolyte pair parameters

can be obtained by regressing solubility data of multiple component

electrolyte systems.

When the electrolyte-molecule and electrolyte-electrolyte pair parameters are

zero, the electrolyte NRTL model reduces to the Debye-Hückel limiting law.

Calculation results with electrolyte-molecule and electrolyte-electrolyte pair

parameters fixed to zero should be adequate for very dilute weak electrolyte

systems; however, for concentrated systems, pair parameters are required

for accurate representation.

See Physical Property Data, Chapter 1, for the pair parameters available from

the electrolyte NRTL model databank. The table contains pair parameters for

some electrolytes in aqueous solution at 100°C. These values were obtained

by using the Aspen Physical Property Data Regression System (DRS) to

regress vapor pressure and mole fraction data at T=100°C with SYSOP15S

(Handbook of Chemistry and Physics, 56th Edition, CRC Press, 1975, p. E-1).

In running the DRS, standard deviations for the temperature (°C), vapor

pressure (mmHg), and mole fractions were set at 0.2, 1.0, and 0.001,

respectively. In addition, complete dissociation of the electrolyte was

assumed for all cases.

ENRTL-SAC

eNRTL-SAC (ENRTLSAC, patent pending) is an extension of the nonrandom

two-liquid segment activity coefficient model (NRTL-SAC, patent pending) by

Chen and Song (Ind. Eng. Chem. Res., 2004, 43, 8354) to include

electrolytes in the solution. It can be used in usable in Aspen Properties and

Aspen Polymers. It is intended for the computation of ionic activity

coefficients and solubilities of electrolytes, organic and inorganic, in common

solvents and solvent mixtures. In addition to the three types of molecular

parameters defined for organic nonelectrolytes in NRTL-SAC (hydrophobicity

X, hydrophilicity Z, and polarity Y- and Y+), an electrolyte parameter, E, is

introduced to characterize both local and long-range ion-ion and ion-molecule

interactions attributed to ionized segments of electrolytes.

In applying the segment contribution concept to electrolytes, a new

conceptual electrolyte segment e corresponding to the electrolyte parameter

E, is introduced. This conceptual segment e would completely dissociate to a

cationic segment (c) and an anionic segment (a), both of unity charge. All

electrolytes, organic or inorganic, symmetric or unsymmetric, univalent or

multivalent, are to be represented with this conceptual uni-univalent

electrolyte segment e together with previously defined hydrophobic segment

x, polar segments y- and y+, and hydrophilic segment z in NRTL-SAC.

A major consideration in the extension of NRTL-SAC for electrolytes is the

treatment of the reference state for activity coefficient calculations. While the

conventional reference state for nonelectrolyte systems is the pure liquid

component, the conventional reference state for electrolytes in solution is the

infinite-dilution aqueous solution and the corresponding activity coefficient is

unsymmetric. The equation for the logarithm of the unsymmetric activity

coefficient of an ionic species is

With

106 2 Thermodynamic Property Models

Where:

I, J = Component index

i, j, m, c, a = Conceptual segment index

m = Conceptual molecular segment, x, y-, y+, z

c = Conceptual cationic segment

a = Conceptual anionic segment

i, j = m,c,a

xI = Mole fraction of component I

rI,i = Number of conceptual segment i containing in component I

xi = Segment mole fraction of conceptual segment i in mixtures

conceptual segments

segments

Aϕ = Debye-Hückel parameter

= Average solvent molecular weight, g/mol

NA = Avogadro’s number

Qe = Absolute electronic charge

= Average solvent dielectric constant

ra = Born radius of anionic segment

The NRTL binary parameters between conceptual molecular segments in are

determined by available VLE and LLE data between reference molecules

defined in NRTLSAC.

Segment (1) x x y- y+ x

Segment (2) y- z z z y+

τ12 1.643 6.547 -2.000 2.000 1.643

segment e. The NRTL binary parameters between conceptual molecular

segments and the electrolyte segment e are determined from literature data

or preset as follows:

Segment (1) x y- y+ z

Segment (2) e e e e

τ12 15 12 12 8.885

τ21 5 -3 -3 -4.549

Each component can have up to five parameters, rI,i (i = x, y-, y+, z, e),

although only one or two of these parameters are needed for most solvents

and ionic species in practice. Since conceptual segments apply to all species,

these five parameters are implemented together as a binary parameter,

NRTLXY(I, i) where I represents a component index and i represents a

conceptual segment index.

Option codes

There are three option codes in ENRTLSAC. The first is used to enable or

disable the Flory-Huggins term. The other two are only used internally and

you should not change their values. The Flory-Huggins term is included by

default in eNRTL-SAC model. You can remove this term using the first option

code. The table below lists the values for the first option code.

0 Flory-Huggins term included (default)

Others Flory-Huggins term removed

References

C.-C. Chen and Y. Song, "Solubility Modeling with a Nonrandom Two-Liquid

Segment Activity Coefficient Model," Ind. Eng. Chem. Res. 43, 8354 (2004).

C.-C. Chen and Y. Song, "Extension of Nonrandom Two-Liquid Segment

Activity Coefficient Model for Electrolytes," Ind. Eng. Chem. Res. 44, 8909

(2005).

Hansen

Hansen is a solubility parameter model and is commonly used in the solvent

selection process. It is based on the regular solution theory and Hansen

solubility parameters. This model has no binary parameters and its application

merely follows the empirical guide like dissolves like.

The Hansen model calculates liquid activity coefficients. The equation for the

Hansen model is:

with

Where:

effect

bonding effect

xi = Mole fraction of component i

R = Gas constant

T = Temperature

The Hansen model does not require binary parameters. For each component,

it has four input parameters.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

DELTAD δid — x — — PRESSURE^0.5

HANVOL Vi — x — — VOLUME

Option codes

The Hansen volume is implemented as an input parameter. If the Hansen

volume is not input by the user it will be calculated by an Aspen Plus internal

method. You can also request the Aspen Plus method using Option Codes in

Aspen Plus Interface. The table below lists the option codes.

0 Hansen volume input by user (default)

Other values Hansen volume calculated by Aspen Plus

Reference

Frank, T. C.; Downey, J. R.; Gupta, S. K. "Quickly Screen Solvents for

Organic Solids," Chemical Engineering Progress 1999, December, 41.

Hansen, C. M. Hansen Solubility Parameters: A User’s Handbook; CRC Press,

2000.

Ideal Liquid

This model is used in Raoult's law. It represents ideality of the liquid phase.

This model can be used for mixtures of hydrocarbons of similar carbon

number. It can be used as a reference to compare the results of other activity

coefficient models.

The equation is:

ln γi = 0

The NRTL model calculates liquid activity coefficients for the following

property methods: NRTL, NRTL-2, NRTL-HOC, NRTL-NTH, and NRTL-RK. It is

recommended for highly non-ideal chemical systems, and can be used for VLE

and LLE applications. The model can also be used in the advanced equation-

of-state mixing rules, such as Wong-Sandler and MHV2.

The equation for the NRTL model is:

Where:

Gij =

τij =

αij =

τii = 0

Gii = 1

aij, bij, eij, and fij are unsymmetrical. That is, aij may not be equal to aji, etc.

cij Mixtures

0.30 Nonpolar substances; nonpolar with polar non-associated liquids; small

deviations from ideality

0.20 Saturated hydrocarbons with polar non-associated liquids and systems that

exhibit liquid-liquid immiscibility

0.47 Strongly self-associated substances with nonpolar substances

The binary parameters aij, bij, cij, dij, eij, and fij can be determined from VLE

and/or LLE data regression. The Aspen Physical Property System has a large

number of built-in binary parameters for the NRTL model. The binary

parameters have been regressed using VLE and LLE data from the Dortmund

Databank. The binary parameters for the VLE applications were regressed

using the ideal gas, Redlich-Kwong, and Hayden O'Connell equations of state.

See Physical Property Data, Chapter 1, for details.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

NRTL/1 aij 0 x -100.0 100.0 —

NRTL/2 bij 0 x -30000 30000.0 TEMPERATURE

NRTL/3 cij 0.30 x 0.0 1.0 —

NRTL/4 dij 0 x -0.02 0.02 TEMPERATURE

NRTL/5 eij 0 x — — TEMPERATURE

NRTL/6 fij 0 x — — TEMPERATURE

The NRTL-2 property method uses data set 2 for NRTL. All other NRTL

methods use data set 1.

References

H. Renon and J.M. Prausnitz, "Local Compositions in Thermodynamic Excess

Functions for Liquid Mixtures," AIChE J., Vol. 14, No. 1, (1968), pp. 135 –

144.

NRTL-SAC Model

NRTL-SAC (patent pending) is a segment contribution activity coefficient

model, derived from the Polymer NRTL model, but usable in Aspen Plus or

Aspen Properties without Aspen Polymers. NRTL-SAC can be used for fast,

qualitative estimation of the solubility of complex organic compounds in

common solvents. Conceptually, the model treats the liquid non-ideality of

mixtures containing complex organic molecules (solute) and small molecules

(solvent) in terms of interactions between three pairwise interacting

conceptual segments: hydrophobic segment (x), hydrophilic segment (z), and

polar segments (y- and y+). In practice, these conceptual segments become

the molecular descriptors used to represent the molecular surface

characteristics of each solute or solvent molecule. Hexane, water, and

acetonitrile are selected as the reference molecules for the hydrophobic,

hydrophilic, and polar segments, respectively. The molecular parameters for

all other solvents can be determined by regression of available VLE or LLE

data for binary systems of solvent and the reference molecules or their

substitutes. The treatment results in four component-specific molecular

parameters: hydrophobicity X, hydrophilicity Z, and polarity Y- and Y+. The

two types of polar segments, Y- and Y+, are used to reflect the wide

variations of interactions between polar molecules and water.

The conceptual segment contribution approach in NRTL-SAC represents a

practical alternative to the UNIFAC functional group contribution approach.

This approach is suitable for use in the industrial practice of carrying out

measurements for a few selected solvents and then using NRTL-SAC to

quickly predict other solvents or solvent mixtures and to generate a list of

suitable solvent systems.

The NRTL-SAC model calculates liquid activity coefficients.

model GMNRTLS and property method NRTL-SAC. This version does not

require the specification of components as oligomers. For the old version, see

NRTLSAC for Segments/Oligomers.

For the model equations, see NRTL-SAC Model Derivation.

Each component can have up to four parameters, rx,I, ry-,I, ry+,I, and rz,I,

representing the equivalent number of segments of each type for the NRTL

activity coefficient model. Only one or two of these molecular parameters are

needed for most solvents in practice. These four molecular parameters are

implemented together as pure parameter XYZE with four elements

representing these four parameters. Values for this parameter are available

for many common solvents in the NRTL-SAC databank.

Parameter Symbol Default MDS Lower Upper Limit Units

Name/ Limit

Element

XYZE/1 rx,I — — — — —

XYZE/2 ry-,I — — — — —

XYZE/3 ry+,I — — — — —

XYZE/4 rz,I — — — — —

XYZE/5 not used — — — — —

NRTL-SAC activity coefficient model for component I is composed of the

combinatorial term, ln γIC, and the residual term, ln γIR:

(1)

equation for the combinatorial entropy of mixing. The residual term, γIR, is

calculated from the local composition (lc) interaction contribution, γIlc, of

Polymer NRTL (Chen, 1993). The Polymer NRTL equation incorporates the

segment interaction concept and it computes activity coefficient for

component I in a solution by summing up contributions to activity coefficient

from all segments that makes up component I.

Flory-Huggins Term

The excess Gibbs free energy from the Flory-Huggins model is given as

follows:

(2)

with

(3)

where I and J denote component index; nI and xJ are the mole number and

mole fraction of component I, respectively; φI is the segment fraction of

component I; and rI is the total number of segments in component I:

(4)

where i denotes the segment-based species index and ri,I is the number of

segment species i in component I.

The activity coefficient of component I from the entropy of mixing can be

calculated as follows:

(5)

The excess Gibbs free energy from local interactions can be written as

follows:

(6)

(7)

(8)

(9)

where G and τ are local binary quantities related to each other by the NRTL

non-random factor parameter α:

(10)

components, we first compute local composition contributions for each

segment. For this purpose, we rewrite Eq. 6 as follows:

(11)

or

(12)

(13)

component I is then computed as the sum of the individual segment

contributions.

(14)

that γIlc = 1 as xI→1 for any component; the normalization can be done as

follows:

(15)

pure component I; it can be calculated as follows:

(16)

(17)

Henry Components

The infinite-dilution activity coefficient in mixed-solvent solutions for Henry

component H is given as follows:

(18)

(19)

(20)

(21)

(22)

(23)

The infinite-dilution activity coefficient of Henry component H in a solvent S

(i.e., xH→0 and xS→1) is given as follows:

(24)

(25)

(26)

This is the original NRTLSAC model added in version 2006, which requires

that components be defined as oligomers. It is retained for compatibility, but

new models should use the NRTL-SAC model.

NRTL-SAC (patent pending) is a segment contribution activity coefficient

model, derived from the Polymer NRTL model, usable in Aspen Properties and

Aspen Polymers. NRTL-SAC can be used for fast, qualitative estimation of the

solubility of complex organic compounds in common solvents. Conceptually,

the model treats the liquid non-ideality of mixtures containing complex

organic molecules (solute) and small molecules (solvent) in terms of

interactions between three pairwise interacting conceptual segments:

hydrophobic segment (x), hydrophilic segment (z), and polar segments (y-

and y+). In practice, these conceptual segments become the molecular

descriptors used to represent the molecular surface characteristics of each

solute or solvent molecule. Hexane, water, and acetonitrile are selected as

the reference molecules for the hydrophobic, hydrophilic, and polar segments,

respectively. The molecular parameters for all other solvents can be

determined by regression of available VLE or LLE data for binary systems of

solvent and the reference molecules or their substitutes. The treatment

results in four component-specific molecular parameters: hydrophobicity X,

hydrophilicity Z, and polarity Y- and Y+. The two types of polar segments, Y-

and Y+, are used to reflect the wide variations of interactions between polar

molecules and water.

The conceptual segment contribution approach in NRTL-SAC represents a

practical alternative to the UNIFAC functional group contribution approach.

This approach is suitable for use in the industrial practice of carrying out

measurements for a few selected solvents and then using NRTL-SAC to

quickly predict other solvents or solvent mixtures and to generate a list of

suitable solvent systems.

The NRTL-SAC model calculates liquid activity coefficients.

The equation for the NRTL-SAC model is:

with

G = exp(-ατ)

Where:

I, J = Component index

i, j, m = Conceptual segment indexx, y-, y+, z

γIR = γIlc = NRTL term for local composition interaction contribution to

γI

φI = Segment mole fraction of component I

xI = Mole fraction of component I

rI,m = Number of conceptual segment m containing in component

I

xi = Segment mole fraction of conceptual segment i in mixtures

conceptual segments

segments

The NRTL binary parameters between conceptual segments in NRTLSAC are

determined by available VLE and LLE data between reference molecules

defined above.

Segment 1 x x y- y+ x

Segment 2 y- z z z y+

τ12 1.643 6.547 -2.000 2.000 1.643

Each component can have up to four parameters, rI,x, rI,y-, rI,y+, and rI,z

although only one or two of these molecular parameters are needed for most

solvents in practice. Since conceptual segments apply to all molecules, these

four molecular parameters are implemented together as a binary parameter,

NRTLXY(I, m) where I represents a component (molecule) index and m

represents a conceptual segment index.

In addition, the Flory-Huggins size parameter, FHSIZE , is used in NRTLSAC

to calculate the effective component size parameter, pI. The Flory-Huggins

combinatorial term can be turned off by setting εI = 0 for each component in

mixtures.

Parameter Symbol Default MDS Lower Upper Units Comment

Name/ Limit Limit

Element

NRTLXY rI,m — — — — — Binary,

symmetric

FHSIZE/1 sI 1.0 — 1E-15 1E15 — Unary

FHSIZE/2 εI 1.0 — -1E10 1E10 — Unary

Option codes

The Flory-Huggins term is included by default in the NRTLSAC model. You can

remove this term using the first option code. The table below lists the values

for this option code.

0 Flory-Huggins term included (default)

Others Flory-Huggins term removed

The molecular parameters are identified for 62 solvents and published.

Solvent name rI,x rI,y- rI,y+ rI,z

ACETIC-ACID 0.045 0.164 0.157 0.217

ACETONE 0.131 0.109 0.513

ACETONITRILE 0.018 0.131 0.883

ANISOLE 0.722

BENZENE 0.607 0.190

1-BUTANOL 0.414 0.007 0.485

2-BUTANOL 0.335 0.082 0.355

N-BUTYL-ACETATE 0.317 0.030 0.330

METHYL-TERT-BUTYL-ETHER 1.040 0.219 0.172

CARBON-TETRACHLORIDE 0.718 0.141

CHLOROBENZENE 0.710 0.424

CHLOROFORM 0.278 0.039

CUMENE 1.208 0.541

CYCLOHEXANE 0.892

1,2-DICHLOROETHANE 0.394 0.691

1,1-DICHLOROETHYLENE 0.529 0.208

1,2-DICHLOROETHYLENE 0.188 0.832

DICHLOROMETHANE 0.321 1.262

Solvent name rI,x rI,y- rI,y+ rI,z

1,2-DIMETHOXYETHANE 0.081 0.194 0.858

N,N-DIMETHYLACETAMIDE 0.067 0.030 0.157

N,N-DIMETHYLFORMAMIDE 0.073 0.564 0.372

DIMETHYL-SULFOXIDE 0.532 2.890

1,4-DIOXANE 0.154 0.086 0.401

ETHANOL 0.256 0.081 0.507

2-ETHOXYETHANOL 0.071 0.318 0.237

ETHYL-ACETATE 0.322 0.049 0.421

ETHYLENE-GLYCOL 0.141 0.338

DIETHYL-ETHER 0.448 0.041 0.165

ETHYL-FORMATE 0.257 0.280

FORMAMIDE 0.089 0.341 0.252

FORMIC-ACID 0.707 2.470

N-HEPTANE 1.340

N-HEXANE 1.000

ISOBUTYL-ACETATE 1.660 0.108

ISOPROPYL-ACETATE 0.552 0.154 0.498

METHANOL 0.088 0.149 0.027 0.562

2-METHOXYETHANOL 0.052 0.043 0.251 0.560

METHYL-ACETATE 0.236 0.337

3-METHYL-1-BUTANOL 0.419 0.538 0.314

METHYL-BUTYL-KETONE 0.673 0.224 0.469

METHYLCYCLOHEXANE 1.162 0.251

METHYL-ETHYL-KETONE 0.247 0.036 0.480

METHYL-ISOBUTYL-KETONE 0.673 0.224 0.469

ISOBUTANOL 0.566 0.067 0.485

N-METHYL-2-PYRROLIDONE 0.197 0.322 0.305

NITROMETHANE 0.025 1.216

N-PENTANE 0.898

1-PENTANOL 0.474 0.223 0.426 0.248

1-PROPANOL 0.375 0.030 0.511

ISOPROPYL-ALCOHOL 0.351 0.070 0.003 0.353

N-PROPYL-ACETATE 0.514 0.134 0.587

PYRIDINE 0.205 0.135 0.174

SULFOLANE 0.210 0.457

TETRAHYDROFURAN 0.235 0.040 0.320

1,2,3,4-TETRAHYDRONAPHTHALENE 0.443 0.555

TOLUENE 0.604 0.304

1,1,1-TRICHLOROETHANE 0.548 0.287

Solvent name rI,x rI,y- rI,y+ rI,z

TRICHLOROETHYLENE 0.426 0.285

M-XYLENE 0.758 0.021 0.316

WATER 1.000

TRIETHYLAMINE 0.557 0.105

1-OCTANOL 0.766 0.032 0.624 0.335

Reference

C.-C. Chen and Y. Song, "Solubility Modeling with a Nonrandom Two-Liquid

Segment Activity Coefficient Model," Ind. Eng. Chem. Res. 43, 8354 (2004).

Using NRTLSAC

NRTLSAC (patent pending) is a segment contribution activity coefficient

model, derived from the Polymer NRTL model, usable in Aspen Properties and

Aspen Polymers. NRTLSAC can be used for fast, qualitative estimation of the

solubility of complex organic compounds in common solvents. For more

information about the model, see NRTLSAC for Segments/Oligomers.

Note: A newer version of NRTL-SAC comes with its own property method

named NRTL-SAC and does not require the specification of a method and

oligomer components as described below.

The NRTLSAC model for Segments/Oligomers in the Aspen Physical Property

System is a liquid activity coefficient model called NRTLSAC. To specify it:

1. On the Properties | Specifications sheet, specify process type ALL.

2. Specify base method NRTLSAC.

In order to use this version of NRTLSAC, all components must be defined as

oligomers. Four conceptual segments also must be defined. On the

Components | Polymers | Oligomers sheet, enter a number for at least

one conceptual segment for each oligomer component, as required by the

definition of an oligomer. These numbers are not used by NRTL-SAC.

On the Properties | Parameters | Binary Interaction | NRTL-1 form,

enter the binary parameters between conceptual segments. In the following

example, the conceptual segments are named X, Y-, Y+, and Z.

Segment 1 X X Y- Y+ X

Segment 2 Y- Z Z Z Y+

AIJ 1.643 6.547 -2.000 2.000 1.643

AJI 1.834 10.949 1.787 1.787 1.834

CIJ 0.2 0.2 0.3 0.3 0.2

enter a non-zero value for at least one of the four parameters for each

component.

Pitzer Activity Coefficient Model

The Pitzer model was developed as an improvement upon an earlier model

proposed by Guggenheim (1935, 1955). The earlier model worked well at low

electrolyte concentrations, but contained discrepancies at higher

concentrations (>0.1M). The Pitzer model resolved these discrepancies,

without resorting to excessive arrays of higher-order terms.

The model can be used for aqueous electrolyte systems, up to 6 molal ionic

strength. It cannot be used for systems with any other solvent or mixed

solvents.

This section provides theoretical background for the model. All model

equations and parameter requirements are included.

The Pitzer model is commonly used in the calculation of activity coefficients

for aqueous electrolytes up to 6 molal ionic strength. Do not use this model if

a non-aqueous solvent exists. Henry's law parameters are required for all

other components in the aqueous solution. The model development and

working equations are provided in the following sections. Parameter

conversion between the Pitzer notation and our notation is also provided.

The Pitzer model in the Aspen Physical Property System involves user-

supplied parameters that are used in the calculation of binary and ternary

parameters for the electrolyte system.

Five elements (P1 through P5) account for the temperature dependencies of

ϕ

parameters β(0), β(1), β(2), β(3), C , θ, and Ψ. These parameters follow the

temperature dependency relation:

Where:

Tref = 298.15 K

The user must:

• Supply these elements for the binary parameters using a Properties |

Parameters | Binary | T-Dependent form.

• Supply these elements for Ψ on the Properties | Parameters | Electrolyte

Ternary form.

• Specify Comp ID i and Comp ID j (and Comp ID k for Ψ) on these forms,

using the same order that appears on the Components Specifications

Selection sheet.

The parameters are summarized in the following table. There is a Pitzer

parameter databank in the Aspen Physical Property System (see Physical

Property Data).

Parameter Provides No. of Default MDS Units

Name P1 - P5 for Elements

Cation-Anion Parameters

GMPTB0 β(0) 5 0 x —

GMPTB1 β(1) 5 0 x —

Parameter Provides No. of Default MDS Units

Name P1 - P5 for Elements

GMPTB2 β(2) 5 0 x —

GMPTB3 β(3) 5 0 x —

GMPTC ϕ 5 0 x —

C

Cation-Cation Parameters

GMPTTH θcc' 5 0 x —

Anion-Anion Parameters

GMPTTH θaa' 5 0 x —

Ternary Parameters

GMPTPS, Ψijk 1 (in each 0 x —

GMPTP1, parameter)

GMPTP2,

GMPTP3,

GMPTP4

Molecule-Ion and Molecule-Molecule Parameters

GMPTB0 β(0) 5 0 x —

GMPTB1 β(1) 5 0 x —

GMPTC ϕ 5 0 x —

C

Model Development

The Pitzer model analyzes "hard-core" effects in the Debye-Hückel theory. It

uses the following expansion as a radial distribution function:

(1)

Where:

gij = Distribution function

r = Radius

qij =

With:

zi = Charge of ion i

Qe = Electron charge

k = Boltzmann's constant

T = Temperature

This radial distribution function is used in the so-called pressure equation that

relates this function and the intermolecular potential to thermodynamic

properties. From this relation you can obtain an expression for the osmotic

coefficient.

Pitzer proposes a general equation for the excess Gibbs energy. The basic

equation is:

(2)

Where:

GE = Excess Gibbs energy

R = Gas constant

T = Temperature

nw = Kilograms of water

mi =

(molality of ion i)

With:

xi = Mole fraction of ion i

xw = Mole fraction of water

Mw = Molecular weight of water (g/mol)

ni = Moles of ion i

The function f(I) is an electrostatic term that expresses the effect of long-

range electrostatic forces between ions. This takes into account the hard-core

effects of the Debye-Hückel theory. This term is discussed in detail in the

following section. The parameters λij are second virial coefficients that

account for the short-range forces between solutes i and j. The parameters

μijk account for the interactions between solutes, i, j, k. For ion-ion

interactions, λij is a function of ionic strength. For molecule-ion or molecule-

molecule interactions this ionic strength dependency is neglected. The

dependence of μijk on ionic strength is always neglected. The matrices λij and

μijk are also taken to be symmetric (that is, λij = λji).

Pitzer modified this expression for the Gibbs energy by identifying

combinations of functions. He developed interaction parameters that can be

evaluated using experimental data. He selected mathematical expressions for

these parameters that best fit experimental data.

Pitzer's model can be applied to aqueous systems of strong electrolytes and

to aqueous systems of weak electrolytes with molecular solutes. These

applications are discussed in the following section.

In the Aspen Physical Property System, this model is applied using the

reference state of infinite dilution solution in water for non-water molecular

solutes and ionic species. The properties such as DHAQFM are obtained at 25

C and 1 atm.

Application of the Pitzer Model to Aqueous Strong

Electrolyte Systems

Pitzer modified his basic equation to make it more useful for data correlation

of aqueous strong electrolytes. He defined a set of more directly observable

parameters to represent combinations of the second and third virial

coefficients. The modified Pitzer equation is:

(3)

zi = Charge of ion i

Subscripts c, c', and a, a' denote cations and anions of the solution. B, C, θ,

and Ψ are interaction parameters. f(I) is an electrostatic term as a function of

ionic strength. The cation-anion parameters B and C are characteristic for an

aqueous single-electrolyte system. These parameters can be determined by

the properties of pure (apparent) electrolytes. B is expressed as a function of

β(0) and β(1), or of β(0), β(2), and β(3) (see equations 11 through 15).

The parameters θ and Ψ are for the difference of interaction of unlike ions of

the same sign from the mean of like ions. These parameters can be measured

from common-ion mixtures. Examples are NaCl + KCl + H2O or NaCl + NaNO3

+ H2O (sic, Pitzer, 1989). These terms are discussed in detail later in this

section.

Fürst and Renon (1982) propose the following expression as the Pitzer

equation for the excess Gibbs energy:

(4)

The difference between equations 3 and 4 is that Pitzer orders cation before

anions. Fürst and Renon do not. All summations are taken over all ions i and j

(both cations and anions). This involves making the parameter matrices Bij,

Cij, θij, and Ψijk symmetric, as follows:

Second-order parameters are written Bij if i and j are ions of different sign. Bij

= 0 if the sign of zi = sign of zj, and Bii = 0. Since cations are not ordered

before anions, Bij = Bji. This eliminates the 2 in the second term in brackets in

Pitzer's original expression (equation 3). Second-order parameters are written

θij if i and j are ions of the same sign. Thus θij = 0 if the sign of zi is different

from the sign of zj, and θii = 0 with θij = θji.

Third-order parameters are written Cij if i and j are ions with different signs.

Cij = 0 if the sign of zi = sign of zj, and Cii = 0 with Cij = Cji. The factor of 2 in

the fifth bracketed term in Pitzer's original expression (equation 3) becomes

ions to make the equation symmetric.

Ψijk is written for three different ions Ψijk = Ψkij = Ψjki , and Ψikk = 0. Ψijk = 0

if the sign of zi =sign of zj =sign of zk. The factor of 1/6 is different from 1/2

in the last term in brackets in Pitzer's original expression. Pitzer distinguishes

between cations and anions. In Pitzer's original model this parameter appears

twice, as Ψcc'a and Ψc'ca. In this modified model, it appears six times, as Ψcc'a;

Ψc'ca; Ψacc'; Ψac'c; Ψcac'; and Ψc'ac. Fürst and Renon's expression, equation 4,

calculates the expressions for activity coefficients and osmotic coefficients.

Pitzer (1975) modified his model by adding the electrostatic unsymmetrical

mixing effects, producing this modified Pitzer equation for the excess Gibbs

energy:

(4a)

The natural logarithm of the activity coefficient for ions is calculated from

equation 4a to give:

(5)

Where θ is neglected and Φij and Φ'ij are the electrostatic unsymmetric mixing

effects:

The X parameters are calculated differently on the option code.

For option code = –1, there is no unsymmetric mixing correction term:

polynomial form:

form:

follows:

Applying:

(6)

(7)

(8)

(9)

So that:

(10)

Hückel constant for the osmotic coefficient, determined from:

(11)

Where:

NA = Avogadro's constant

dw = Water density

1.2.

B and B' need expressions so that equations 5 and 6 can completely be solved

for the activity coefficients. The parameter B is determined differently for

different electrolyte pairings. For 1-n electrolytes (1-1, 1-2, 2-1, and so on)

the following expression gives the parameter B:

(12)

with α1=2.0.

For n-m electrolytes, n and m>1 (2-2, 2-3, 3-4, and so on), B is determined

by the following expression:

(13)

By taking appropriate derivatives, expressions for B' can be derived for 1–n

electrolytes:

(14)

(15)

The parameters β(0), β(1), β(2), β(3) and also C, θ, and Ψ can be found in

Pitzer's articles .

After the activity coefficients are calculated, they can be converted to the

mole fraction scale from the molality scale by the following relations:

For solutes:

(16)

(17)

Where:

Application of the Pitzer Model to Aqueous

Electrolyte Systems with Molecular Solutes

In aqueous weak electrolyte systems with molecular solutes, the second and

third virial coefficients in the basic Pitzer equation for molecule-ion and

molecule-molecule interactions must be considered. The following extensions

of Pitzer's interaction parameters are made.

The second-order parameters Bij are extended to include molecule-molecule

and molecule-ion interaction parameters.

interactions. The following expressions relate Ψijk to Pitzer's original μijk:

Ψiii = 6μiii

However, molecule-molecule interactions were not taken into account by

Pitzer and coworkers. So μiii is an artificially introduced quantity.

The equations for activity coefficients and the Gibbs free energy are the same

as equations 3 through 6.

Parameters

The Pitzer model in the Aspen Physical Property System involves user-

supplied parameters. These parameters are used in the calculation of binary

and ternary parameters for the electrolyte system. These parameters include

ϕ

the cation-anion parameters β(0), β(1), β(2), β(3) and C , cation-cation

parameter θcc', anion-anion parameter θaa', cation1-cation2-common anion

parameter Ψcc'a, anion1-anion2-common cation parameter Ψcaa', and the

ϕ

molecule-ion and molecule-molecule parameters β(0), β(1), and, C . The

parameter names in the Aspen Physical Property System and their

requirements are discussed in Pitzer Activity Coefficient Model.

Parameter Conversion

For n-m electrolytes, n and m>1 (2-2, 2-3, 3-4, and so on), the parameter

β(3) corresponds to Pitzer's β(1). β(2) is the same in both the Aspen Physical

Property System and original Pitzer models. Pitzer refers to the n-m

electrolyte parameters as β(1), β(2), β(0). β(0) and β(2) retain their meanings in

both models, but Pitzer's β(1) is β(3) in the Aspen Physical Property System. Be

careful to make this distinction when entering n-m electrolyte parameters.

ϕ

Pitzer often gives values of β(0), β(1), β(2), β(3), and C that are corrected by

some factors (see Pitzer and Mayorga (1973) for examples). These factors

originate from one of Pitzer's earlier expressions for the excess Gibbs energy:

(18)

Where:

=

nc = Mole number of cation

Here β(0), β(1), β(2), and β(3) are multiplied by a factor of 2ncna. C is multiplied

by a factor of 2(ncna)3/2.

Aspen Physical Property System accounts for these correcting factors. Enter

the parameters without their correcting factors.

For example, Pitzer gives the values of parameters for MgCl2 as:

4/3β(0) = 0.4698

4/3β(1) = 2.242

= 0.00979

= 0.3524

= 1.6815

= 0.00520

Parameter Sources

Binary and ternary parameters for the Pitzer model for various electrolyte

systems are available from Pitzer's series on the thermodynamics of

electrolytes. These papers and the electrolyte parameters they give are:

Reference Parameters available

ϕ

(Pitzer, 1973) Binary parameters (β(0), β(1), C ) for 13

dilute aqueous electrolytes

(Pitzer and Mayorga, 1973) Binary parameters for 1-1 inorganic

electrolytes, salts of carboxylic acids (1-1),

tetraalkylammonium halids, sulfonic acids

and salts, additional 1-1 organic salts, 2-1

inorganic compounds, 2-1 organic

electrolytes, 3-1 electrolytes, 4-1 and 5-1

electrolytes

(Pitzer and Mayorga, 1974) Binary parameters for 2-2 electrolytes in

water at 25°C

(Pitzer and Kim, 1974) Binary and ternary parameters for mixed

electrolytes, binary mixtures without a

common ion, mixed electrolytes with three

or more solutes

Reference Parameters available

(Pitzer, 1975) Ternary parameters for systems mixing

doubly and singly charged ions

(Pitzer and Silvester, 1976) Parameters for phosphoric acid and its buffer

solutions

(Pitzer, Roy and Silvester, 1977) Parameters and thermodynamic properties

for sulfuric acid

(Silvester and Pitzer, 1977) Data for NaCl and aqueous NaCl solutions

(Pitzer, Silvester, and Peterson, 1978) Rare earth chlorides, nitrates, and

perchlorates

(Peiper and Pitzer, 1982) Aqueous carbonate solutions, including

mixtures of sodium carbonate, bicarbonate,

and chloride

(Phutela and Pitzer, 1983) Aqueous calcium chloride

(Conceicao, de Lima, and Pitzer, 1983) Saturated aqueous solutions, including

mixtures of sodium chloride, potassium

chloride, and cesium chloride

(Pabalan and Pitzer, 1987) Parameters for polynomial unsymmetric

mixing term

(Kim and Frederick, 1988) Parameters for integral unsymmetric mixing

term

Pitzer References

Conceicao, M., P. de Lima, and K.S. Pitzer, "Thermodynamics of Saturated

Aqueous Solutions Including Mixtures of NaCl, KCl, and CsCl, "J. Solution

Chem, Vol. 12, No. 3, (1983), pp. 171-185.

Fürst, W. and H. Renon, "Effects of the Various Parameters in the Application

of Pitzer's Model to Solid-Liquid Equilibrium. Preliminary Study for Strong 1-1

Electrolytes," Ind. Eng. Chem. Process Des. Dev., Vol. 21, No. 3, (1982),

pp. 396-400.

Guggenheim, E.A., Phil. Mag., Vol. 7, No. 19, (1935), p. 588.

Guggenheim, E.A. and J.C. Turgeon, Trans. Faraday Soc., Vol. 51, (1955), p.

747.

Kim, H. and W.J. Frederick, "Evaluation of Pitzer Ion Interaction Parameters

of Aqueous Mixed Electrolyte Solution at 25C, Part 2: Ternary Mixing

Parameters," J. Chem. Eng. Data, 33, (1988), pp. 278-283.

Pabalan, R.T. and K.S. Pitzer, "Thermodynamics of Concentrated Electrolyte

Mixtures and the Prediction of Mineral Solubilities to High Temperatures for

Mixtures in the system Na-K-Mg-Cl-SO4-OH-H2O," Geochimica Acta, 51,

(1987), pp. 2429-2443.

Peiper, J.C. and K.S. Pitzer, "Thermodynamics of Aqueous Carbonate

Solutions Including Mixtures of Sodium Carbonate, Bicarbonate, and

Chloride," J. Chem. Thermodynamics, Vol. 14, (1982), pp. 613-638.

Phutela, R.C. and K.S. Pitzer, "Thermodynamics of Aqueous Calcium

Chloride," J. Solution Chem., Vol. 12, No. 3, (1983), pp. 201-207.

Pitzer, K.S., "Thermodynamics of Electrolytes. I. Theoretical Basis and

General Equations, " J. Phys. Chem., Vol. 77, No. 2, (1973), pp. 268-277.

Pitzer, K.S., J. Solution Chem., Vol. 4, (1975), p. 249.

Pitzer, K.S., "Fluids, Both Ionic and Non-Ionic, over Wide Ranges of

Temperature and Composition," J. Chen. Thermodynamics, Vol. 21, (1989),

pp. 1-17. (Seventh Rossini lecture of the commission on Thermodynamics of

the IUPAC, Aug. 29, 1988, Prague, ex-Czechoslovakia).

Pitzer, K.S. and J.J. Kim, "Thermodynamics of Electrolytes IV; Activity and

Osmotic Coefficients for Mixed Electrolytes," J.Am. Chem. Soc., Vol. 96

(1974), p. 5701.

Pitzer, K.S. and G. Mayorga, "Thermodynamics of Electrolytes II; Activity and

Osmotic Coefficients for Strong Electrolytes with One or Both Ions Univalent,"

J. Phys. Chem., Vol. 77, No. 19, (1973), pp. 2300-2308.

Pitzer, K.S. and G. Mayorga, J. Solution Chem., Vol. 3, (1974), p. 539.

Pitzer, K.S., J.R. Peterson, and L.F. Silvester, "Thermodynamics of

Electrolytes. IX. Rare Earth Chlorides, Nitrates, and Perchlorates, "J. Solution

Chem., Vol. 7, No. 1, (1978), pp. 45-56.

Pitzer, K.S., R.N. Roy, and L.F. Silvester, "Thermodynamics of Electrolytes 7

Sulfuric Acid," J. Am. Chem. Soc., Vol. 99, No. 15, (1977), pp. 4930-4936.

Pitzer, K.S. and L.F. Silvester, J. Solution Chem., Vol. 5, (1976), p. 269.

Silvester, L.F. and K.S. Pitzer, "Thermodynamics of Electrolytes 8 High-

Temperature Properties, Including Enthalpy and Heat Capacity, With

Application to Sodium Chloride," J. Phys. Chem., Vol. 81, No. 19, (1977), pp.

1822-1828.

This model represents activity coefficient as an empirical function of

composition and temperature. It is used frequently in metallurgical

applications where multiple liquid and solid solution phases can exist.

The equation is:

Where:

Ai =

Bi =

Ci =

Di =

Ei =

For any component i, the value of the activity coefficient can be fixed:

γi = fi

This model is not part of any property method. To use it:

3. On the Properties | Specifications sheet, specify an activity coefficient

model, such as NRTL.

4. Click the Properties | Property Methods folder.

5. In the Object Manager, click New.

6. In the Create New ID dialog box, enter a name for the new method.

7. In the Base Property Method field, select NRTL.

8. Click the Models tab.

9. Change the Model Name for GAMMA from GMRENON to GMPOLY.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

GMPLYP/1 ai1 0 x — — —

GMPLYP/2 ai2 0 x — — —

GMPLYP/3 ai3 0 x — — —

GMPLYP/4 bi1 0 x — — —

GMPLYP/5 bi2 0 x — — —

GMPLYP/6 bi3 0 x — — —

GMPLYP/7 ci1 0 x — — —

GMPLYP/8 ci2 0 x — — —

GMPLYP/9 ci3 0 x — — —

GMPLYP/10 di1 0 x — — —

GMPLYP/11 di2 0 x — — —

GMPLYP/12 di3 0 x — — —

GMPLYP/13 ei1 0 x — — —

GMPLYP/14 ei2 0 x — — —

GMPLYP/15 ei3 0 x — — —

GMPLYO fi — x — — —

Component | T-Dependent sheet, you can only enter the first 12 elements.

If you want to specify values for elements 13 to 15, you should go to the

Flowsheeting Options | Add-Input | Add After sheet in Aspen Plus or the

Add-Input | Add-Input | Add After sheet in Aspen Properties, and enter

the values of all 15 elements as in the following example:

PROP-DATA GMPLYP-1

IN-UNITS SI

PROP-LIST GMPLYP

PVAL WATER 0.0 1.5 0.0 &

0.0 0.0 0.0 &

0.0 0.0 0.0 &

0.0 0.0 0.0 &

0.0 16. 0.0

Redlich-Kister

This model calculates activity coefficients. It is a polynomial in the difference

between mole fractions in the mixture. It can be used for liquid and solid

mixtures (mixed crystals).

The equation is:

Where:

nc = Number of components

A1,ij = aij / T + bij

A2,ij = cij / T + dij

A3,ij = eij / T + fij

A4,ij = gij / T + hij

A5,ij = mij / T + nij

An,ii = An,jj = 0.0

An,ji = An,ij(-1)(n-1)

An,kj = An,jk(-1)(n-1)

For any component i, the value of the activity coefficient can be fixed:

γi = vi

Parameter Name/ Symbol Default MDS Lower Upper Units

Element Limit Limit

GMRKTB/1 aij 0 x — — —

GMRKTB/2 bij 0 x — — —

GMRKTB/3 cij 0 x — — —

GMRKTB/4 dij 0 x — — —

GMRKTB/5 eij 0 x — — —

GMRKTB/6 fij 0 x — — —

GMRKTB/7 gij 0 x — — —

GMRKTB/8 hij 0 x — — —

GMRKTB/9 mij 0 x — — —

GMRKTB/10 nij 0 x — — —

GMRKTO vi — x — — —

Scatchard-Hildebrand

The Scatchard-Hildebrand model calculates liquid activity coefficients. It is

used in the CHAO-SEA property method and the GRAYSON property method.

The equation for the Scatchard-Hildebrand model is:

Where:

Aij =

ϕi =

Vm*,l =

Name/Element Limit Limit

TC Tci — x 5.0 2000.0 TEMPERATURE

DELTA δi — x 103 105 SOLUPARAM

VOLUME

GMSHVL Vi*,l x 0.01 1.0 MOLE-

VOLUME

Three-Suffix Margules

This model can be used to describe the excess properties of liquid and solid

solutions. It does not find much use in chemical engineering applications, but

is still widely used in metallurgical applications. Note that the binary

parameters for this model do not have physical significance.

The equation is:

For any component i, the value of the activity coefficient can be fixed:

γi = di

Parameter Name/ Symbol Default MDS Lower Upper Units

Element Limit Limit

GMMRGB/1 aij 0 x — — TEMPERATURE

GMMRGB/2 bij 0 x — — —

GMMRGB/3 cij 0 x — — —

Parameter Name/ Symbol Default MDS Lower Upper Units

Element Limit Limit

GMMRGO di — x — — —

References

M. Margules, "Über die Zusammensetzung der gesättigten Dämpfe von

Mischungen," Sitzungsber. Akad. Wiss. Vienna, Vol. 104, (1895), p. 1293.

D.A. Gaskell, Introduction to Metallurgical Thermodyanics, 2nd ed., (New

York: Hemisphere Publishing Corp., 1981), p. 360.

R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and

Liquids, 4th ed., (New York: McGraw-Hill, 1987).

The UNIFAC model calculates liquid activity coefficients for the following

property methods: UNIFAC, UNIF-HOC, and UNIF-LL. Because the UNIFAC

model is a group-contribution model, it is predictive. All published group

parameters and group binary parameters are stored in the Aspen Physical

Property System.

The equation for the original UNIFAC liquid activity coefficient model is made

up of a combinatorial and residual term:

ln γ = ln γic + ln γir

ln γic =

and

Where nc is the number of components in the mixture. The coordination

number z is set to 10. The parameters ri and qi are calculated from the group

volume and area parameters:

and

number of groups in the mixture.

The residual term is:

Γk is the activity coefficient of a group at mixture composition, and Γki is the

activity coefficient of group k in a mixture of groups corresponding to pure i.

The parameters Γk and Γki are defined by:

With:

And:

Name/Element Limit Limit

UFGRP (k,νk, m, νm, ...) — — — — —

GMUFQ Qk — — — — —

GMUFR Rk — — — — —

GMUFB bkn — — — — TEMPERATURE

The parameter UFGRP stores the UNIFAC functional group number and

number of occurrences of each group. UFGRP is stored in the Aspen Physical

Property System pure component databank for most components. For

nondatabank components, enter UFGRP on the Properties Molecular Structure

Functional Group sheet. See Physical Property Data, Chapter 3, for a list of

the UNIFAC functional groups.

UNIFAC-PSRK

The PSRK property method uses GMUFPSRK, the UNIFAC-PSRK model, which

is a variation on the standard UNIFAC model. UNIFAC-PSRK has special

groups defined for the light gases CO2, H2, NH3, N2, O2, CO, H2S, and argon,

and the group binary interaction parameters are temperature-dependent,

using the values in parameter UNIFPS, instead of the constant value from

GMUFB used above, so that:

Where a, b, and c are the three elements of UNIFPS.

References

Aa. Fredenslund, J. Gmehling and P. Rasmussen, "Vapor-Liquid Equilibria

using UNIFAC," (Amsterdam: Elsevier, 1977).

Aa. Fredenslund, R.L. Jones and J.M. Prausnitz, AIChE J., Vol. 21, (1975), p.

1086.

H.K. Hansen, P. Rasmussen, Aa. Fredenslund, M. Schiller, and J. Gmehling,

"Vapor-Liquid Equilibria by UNIFAC Group Contribution. 5 Revision and

Extension", Ind. Eng. Chem. Res., Vol. 30, (1991), pp. 2352-2355.

The UNIFAC modification by Gmehling and coworkers (Weidlich and

Gmehling, 1987; Gmehling et al., 1993), is slightly different in the

combinatorial part. It is otherwise unchanged compared to the original

UNIFAC:

With:

Name/Element Limit Limit

UFGRPD (k,νk, m, νm, ...) — — — — —

GMUFDQ Qk — — — — —

GMUFDR Rk — — — — —

UNIFDM/1 amn,1 0 — — — TEMPERATURE

UNIFDM/2 amn,2 0 — — — TEMPERATURE

UNIFDM/3 amn,3 0 — — — TEMPERATURE

The parameter UFGRPD stores the group number and the number of

occurrences of each group. UFGRPD is stored in the Aspen Physical Property

System pure component databank. For nondatabank components, enter

UFGRPD on the Properties Molecular Structure Functional Group sheet. See

Physical Property Data, Chapter 3, for a list of the Dortmund modified UNIFAC

functional groups.

References

U. Weidlich and J. Gmehling, "A Modified UNIFAC Model 1. Prediction of VLE,

hE and ," Ind. Eng. Chem. Res., Vol. 26, (1987), pp. 1372–1381.

J. Gmehling, J. Li, and M. Schiller, "A Modified UNIFAC Model. 2. Present

Parameter Matrix and Results for Different Thermodynamic Properties," Ind.

Eng. Chem. Res., Vol. 32, (1993), pp. 178–193.

The equations for the "temperature-dependent UNIFAC" (Larsen et al., 1987)

are similar to the original UNIFAC:

With:

Where Γk and Γki have the same meaning as in the original UNIFAC, but

defined as:

With:

The temperature dependency of a is described by a function instead of a

constant:

Name/Element Limit Limit

UFGRPL (k,νk, m, νm, ...) — — — — —

GMUFLQ Qk — — — — —

GMUFLR Rk — — — — —

UNIFLB/1 amn,1 0 — — — TEMPERATURE

UNIFLB/2 amn,2 0 — — — TEMPERATURE

UNIFLB/3 amn,3 0 — — — TEMPERATURE

The parameter UFGRPL stores the modified UNIFAC functional group number

and the number of occurrences of each group. UFGRPL is stored in the Aspen

Physical Property System pure component databank. For nondatabank

components, enter UFGRP on the Properties | Molecular Structure |

Functional Group sheet. See Physical Property Data, Chapter 3, for a list of

the Larsen modified UNIFAC functional groups.

Reference: B. Larsen, P. Rasmussen, and Aa. Fredenslund, "A Modified

UNIFAC Group-Contribution Model for Prediction of Phase Equilibria and Heats

of Mixing," Ind. Eng. Chem. Res., Vol. 26, (1987), pp. 2274 – 2286.

The UNIQUAC model calculates liquid activity coefficients for these property

methods: UNIQUAC, UNIQ-2, UNIQ-HOC, UNIQ-NTH, and UNIQ-RK. It is

recommended for highly non-ideal chemical systems, and can be used for VLE

and LLE applications. This model can also be used in the advanced equations

of state mixing rules, such as Wong-Sandler and MHV2.

The equation for the UNIQUAC model is:

Where:

θi =

θi ' =

Φi =

li =

ti ' =

τij =

z = 10

aij, bij, cij, and dij are unsymmetrical. That is, aij may not be equal to aji, etc.

Absolute temperature units are assumed for the binary parameters aij, bij, cij,

dij, and eij.

can be determined from VLE and/or LLE data regression. The Aspen Physical

Property System has a large number of built-in parameters for the UNIQUAC

model. The binary parameters have been regressed using VLE and LLE data

from the Dortmund Databank. The binary parameters for VLE applications

were regressed using the ideal gas, Redlich-Kwong, and Hayden-O'Connell

equations of state. See Physical Property Data, Chapter 1, for details.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

GMUQR ri — x — — —

GMUQQ qi — x — — —

GMUQQ1 qi' q x — — —

UNIQ/1 aij 0 x -50.0 50.0 —

UNIQ/2 bij 0 x -15000.0 15000.0 TEMPERATURE

UNIQ/3 cij 0 x — — TEMPERATURE

UNIQ/4 dij 0 x — — TEMPERATURE

UNIQ/5 Tlower 0K x — — TEMPERATURE

UNIQ/6 Tupper 1000 K x — — TEMPERATURE

UNIQ/7 eij 0 x — — TEMPERATURE

UNIQ.

The UNIQ-2 property method uses data set 2 for UNIQ. All other UNIQUAC

methods use data set 1.

References

D.S. Abrams and J.M. Prausnitz, "Statistical Thermodynamics of liquid

mixtures: A new expression for the Excess Gibbs Energy of Partly or

Completely Miscible Systems," AIChE J., Vol. 21, (1975), p. 116.

A. Bondi, "Physical Properties of Molecular Crystals, Liquids and Gases," (New

York: Wiley, 1960).

Simonetty, Yee and Tassios, "Prediction and Correlation of LLE," Ind. Eng.

Chem. Process Des. Dev., Vol. 21, (1982), p. 174.

Van Laar Activity Coefficient Model

The Van Laar model (Van Laar 1910) calculates liquid activity coefficients for

the property methods: VANLAAR, VANL-2, VANL-HOC, VANL-NTH, and VANL-

RK. It can be used for highly nonideal systems.

Where:

zi =

Ai =

Bi =

Ci =

Aij =

Cij =

Cij = Cji

Aii = Bii = Cii = 0

aij and bij are unsymmetrical. That is, aij may not be equal to aji, and bij may

not be equal to bji.

Parameters Symbol Default MDS Lower Limit Upper Units

Name/Element Limit

VANL/1 aij 0 x -50.0 50.0 —

VANL/2 bij 0 x -15000.0 15000.0 TEMPERATURE

VANL/3 cij 0 x -50.0 50.0 —

VANL/4 dij 0 x -15000.0 15000.0 TEMPERATURE

The VANL-2 property method uses data set 2 for VANL. All other Van Laar

methods use data set 1.

References

J.J. Van Laar, "The Vapor Pressure of Binary Mixtures," Z. Phys. Chem., Vol.

72, (1910), p. 723.

R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and

Liquids, 4th ed. (New York: McGraw-Hill, 1987).

Wagner Interaction Parameter

The Wagner Interaction Parameter model calculates activity coefficients. This

model is used for dilute solutions in metallurgical applications.

The relative activity coefficient with respect to the reference activity

coefficient of a solute i (in a mixture of solutes i, j, and l and solvent A) is:

Where:

For any component i, the value of the activity coefficient can be fixed:

γi = gi

This model is recommended for dilute solutions.

Parameter Name/ Symbol Default MDS Lower Upper Units

Element Limit Limit

GMWIPR/1 ai 0 x — — TEMPERATURE

GMWIPR/2 bi 0 x — — —

GMWIPR/3 ci 0 x — — —

GMWIPB/1 dij 0 x — — TEMPERATURE

GMWIPB/2 eij 0 x — — —

GMWIPB/3 fij 0 x — — —

GMWIPO gi — x — — —

GMWIPS — 0 x — — —

GMWIPS is used to identify the solvent component. You must set GMWIPS to

1.0 for the solvent component. This model allows only one solvent.

References

A.D. Pelton and C. W. Bale, "A Modified Interaction Parameter Formalism for

Non-Dilute Solutions," Metallurgical Transactions A, Vol. 17A, (July 1986),

p. 1211.

Wilson Activity Coefficient Model

The Wilson model calculates liquid activity coefficients for the following

property methods: WILSON, WILS2, WILS-HOC, WILS-NTH, WILS-RK, WILS-

HF, WILS-LR, and WILS-GLR. It is recommended for highly nonideal systems,

especially alcohol-water systems. It can also be used in the advanced

equation-of-state mixing rules, such as Wong-Sandler and MHV2. This model

cannot be used for liquid-liquid equilibrium calculations.

The equation for the Wilson model is:

Where:

†

ln Aij =

equilibrium and enthalpy data. aij, bij, cij, dij, and eij are unsymmetrical. That

is, aij may not be equal to aji, etc.

The binary parameters aij, bij, cij, dij, and eij must be determined from data

regression or VLE and/or heat-of-mixing data. The Aspen Physical Property

System has a large number of built-in binary parameters for the Wilson

model. The binary parameters have been regressed using VLE data from the

Dortmund Databank. The binary parameters were regressed using the ideal

gas, Redlich-Kwong, and Hayden-O'Connell equations of state. See Physical

Property Data, Chapter 1, for details.

Parameter Symbol Default MDS Lower Limit Upper Units

Name/Element Limit

WILSON/1 aij 0 x -50.0 50.0 —

WILSON/2 bij 0 x -15000.0 15000.0 TEMPERATURE

††

WILSON/3 cij 0 x -— — TEMPERATURE

††

WILSON/4 dij 0 x — — TEMPERATURE

††

WILSON/5 Tlower 0K x — — TEMPERATURE

WILSON/6 Tupper 1000 K x — — TEMPERATURE

WILSON/7 eij 0 x — — TEMPERATURE

††

The WILS-2 property method uses data set 2 for WILSON. All other Wilson

methods use data set 1.

† In the original formulation of the Wilson model, aij = ln Vj/Vi, cij = dij = eij =

0, and

bij = -(λij - λii)/R, where Vj and Vi are pure component liquid molar volume at

25°C.

†† If any of biA, ciA, and eiA are non-zero, absolute temperature units are

assumed for all coefficients. If biA, ciA, and eiA are all zero, the others are

interpreted in input units. The temperature limits are always interpreted in

input units.

References

G.M. Wilson, J. Am. Chem. Soc., Vol. 86, (1964), p. 127.

This Wilson model (used in the method WILS-VOL) calculates liquid activity

coefficients using the original formulation of Wilson (Wilson 1964) except that

liquid molar volume is calculated at system temperature, instead of at 25°C.

It is recommended for highly nonideal systems, especially alcohol water

systems. It can be used in any activity coefficient property method or in the

advanced equation of state mixing rules, such as Wong Sandler and MHV2.

This model cannot be used for liquid liquid equilibrium calculations.

The equation for the Wilson model is:

Where:

†

ln Aij =

Vj and Vi are pure component liquid molar volume at the system temperature

calculated using the Rackett/DIPPR/IK-CAPE model. The extended form of ln

Aij provides more flexibility in fitting phase equilibrium and enthalpy data. aij,

bij, cij, dij, and eij are unsymmetrical. That is, aij may not be equal to aji, etc.

The binary parameters aij, bij, cij, dij, and eij must be determined from data

regression of VLE and/or heat-of-mixing data. There are no built in binary

parameters for this model.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

WSNVOL/1 aij 0 x -50.0 50.0 —

WSNVOL/2 bij 0 x -15000.0 15000.0 TEMPERATURE

††

WSNVOL/3 cij 0 x -— — TEMPERATURE

††

WSNVOL/4 dij 0 x — — TEMPERATURE

††

WSNVOL/5 eij 0 x — — TEMPERATURE

††

WSNVOL/6 Tlower 0K x — — TEMPERATURE

WSNVOL/7 Tupper 1000 K x — — TEMPERATURE

required.

† In the original formulation of the Wilson model, aij = cij = dij = eij = 0 and

†† If any of biA, ciA, and eiA are non-zero, absolute temperature units are

assumed for all coefficients. If biA, ciA, and eiA are all zero, the others are

interpreted in input units. The temperature limits are always interpreted in

input units.

Reference: G.M. Wilson, J. Am. Chem. Soc., Vol. 86, (1964), p. 127.

Fugacity Models

The Aspen Physical Property System has the following built-in vapor pressure

and liquid fugacity models. This section describes the vapor pressure and

liquid fugacity models available.

Model Type

Extended Antoine/Wagner/IK-CAPE Vapor pressure

API Sour Vapor pressure

Braun K-10 Vapor pressure

Chao-Seader Fugacity

Grayson-Streed Fugacity

Kent-Eisenberg Fugacity

Maxwell-Bonnell Vapor pressure

Solid Antoine Vapor pressure

Extended Antoine/Wagner/PPDS/IK-CAPE

Liquid Vapor Pressure Model

The Aspen Physical Property System has several submodels for calculating

vapor pressure of a liquid. It uses parameter THRSWT/3 to determine which

submodel is used. See Pure Component Temperature-Dependent Properties

for details.

If THRSWT/3 is Then this equation is used

0 Extended Antoine

200 BARIN

301 Wagner

302 PPDS Modified Wagner

400 PML

401 IK-CAPE

501 NIST TDE Polynomial

502 NIST Wagner 25

Extended Antoine Equation

Parameters for many components are available for the extended Antoine

equation from the Aspen Physical Property System pure component databank.

This equation can be used whenever the parameter PLXANT is available.

The equation for the extended Antoine vapor pressure model is:

Parameter Symbol Default MDS Lower Upper Units

Name/ Element Limit Limit

PLXANT/1 C1i x PRESSURE,

TEMPERATURE

PLXANT/2 C2i x TEMPERATURE

If C5i, C6i, or C7i is non-zero, absolute temperature units are assumed for all

coefficients C1i through C7i. The temperature limits are always in user input

units.

The Wagner vapor pressure equation is the best equation for correlation. The

equation can be used if the parameter WAGNER is available:

Where:

Tri = T / Tci

pri*,l = pi*,l / pci

Linear extrapolation of ln pi*,l versus T occurs outside of temperature bounds.

temperature units.

The PPDS equation also uses the same parameter WAGNER as the standard

Wagner equation:

Where:

Tri = T / Tci

pri*,l = pi*,l / pci

Linear extrapolation of ln pi*,l versus T occurs outside of temperature bounds.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

WAGNER/1 C1i x

WAGNER/2 C2i 0 x

WAGNER/3 C3i 0 x

WAGNER/4 C4i 0 x

TC Tci TEMPERATURE

PC pci PRESSURE

This equation is the same as the PPDS Modified Wagner equation above, but

it uses parameter WAGNER25 instead of WAGNER, and it uses critical

properties from this parameter set also.

Where:

Tri = T / Tci

Linear extrapolation of ln pi*,l versus T occurs outside of temperature bounds.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

WAGNER25/1 C1i x

WAGNER25/2 C2i 0 x

WAGNER25/3 C3i 0 x

WAGNER25/4 C4i 0 x

WAGNER25/5 ln pci 0 x

The IK-CAPE model is a polynomial equation. If the parameter PLPO is

available, the Aspen Physical Property System can use the IK-CAPE vapor

pressure equation:

Linear extrapolation of ln pi*,l versus T occurs outside of temperature bounds.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

PLPO/1 C1i X PRESSURE

TEMPERATURE

PLPO/2, ..., 10 C2i , ..., C10i 0 X TEMPERATURE

The PML vapor pressure equations are modified versions of the Antoine and

Wagner equations. Each equation comes in two alternate forms, identical

except for the use of natural or base-10 logarithms. Parameter LNVPEQ/1

specifies the number of the equation used. Each equation uses a separate

parameter: LNVP1 for equation 1, LOGVP1 for 2, LNPR1 for 3, LOGPR1 for 4,

LNPR2 for 5, and LOGPR2 for 6.

Equation 1 (natural logarithm) and 2 (base 10 logarithm):

Where:

Tri = T / Tci

pri*,l = pi*,l / pci

LNVPEQ/2 and LNVPEQ/3 are the lower and upper temperature limits,

respectively.

In equations 1-4, if elements 4, 7, or 8 are non-zero, absolute temperature

units are assumed for all elements.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

LNVP1/1, ...,8 C1i, ..., C8i x PRESSURE

TEMPERATURE

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

LOGVP1/1, ..., 8 C1i, ..., C8i x PRESSURE

TEMPERATURE

LNPR1/1, ..., 8 C1i, ..., C8i x PRESSURE

TEMPERATURE

LOGPR1/1, ..., 8 C1i, ..., C8i x PRESSURE

TEMPERATURE

LNPR2/1,2 C1i, C2i x

LNVPEQ/1 (equation

number)

LNVPEQ/2 Tlower 0 X TEMPERATURE

TC Tci TEMPERATURE

PC pci PRESSURE

This equation can be used for calculating vapor pressure when parameter

PLTDEPOL is available.

If elements 2, 3, 6, or 8 are non-zero, absolute temperature units are

assumed for all elements.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

PLTDEPOL/1 C1i X

PLTDEPOL/3 C3i 0 X

References

Reid, Prausnitz, and Poling, The Properties of Gases and Liquids, 4th ed.,

(New York: McGraw-Hill, 1987).

Harlacher and Braun, "A Four-Parameter Extension of the Theorem of

Corresponding States," Ind. Eng. Chem. Process Des. Dev., Vol. 9, (1970), p.

479.

W. Wagner, Cryogenics, Vol. 13, (1973), pp. 470-482.

D. Ambrose, M. B. Ewing, N. B. Ghiassee, and J. C. Sanchez Ochoa "The

ebulliometric method of vapor-pressure measurement: vapor pressures of

benzene, hexafluorobenzene, and naphthalene," J. Chem. Thermodyn. 22

(1990), p. 589.

The API Sour model is based on the API sour water model for correlating the

ammonia, carbon dioxide, and hydrogen sulfide volatilities from aqueous sour

water system. The model assumes aqueous phase chemical equilibrium

reactions involving CO2, H2S, and NH3.

The model is applicable from 20 C to 140 C. The authors developed the model

using available phase equilibrium data and reported average errors between

the model and measured partial pressure data as follows

Compound Average Error, %

Up to 60 C Above 60 C

Ammonia 10 36

Carbon dioxide 11 24

Hydrogen sulfide 12 29

Detail of the model is described in the reference below and is too involved to

be reproduced here.

Reference

New Correlation of NH3, CO2, and H2S Volatility Data from Aqueous Sour

Water Systems, API Publication 955, March 1978 (American Petroleum

Institute).

The BK10 model uses the Braun K-10 K-value correlations, which were

developed from the K10 charts (K-values at 10 psia) for both real and pseudo

components. The form of the equation used is an extended Antoine vapor

pressure equation with coefficients specific to real components and pseudo

component boiling ranges.

This method is strictly applicable to heavy hydrocarbons at low pressures.

However, our model includes coefficients for a large number of hydrocarbons

and light gases. For pseudocomponents the model covers boiling ranges 450

– 700 K (350 – 800F). Heavier fractions can also be handled using the

methods developed by AspenTech.

References

B.C. Cajander, H.G. Hipkin, and J.M. Lenoir, "Prediction of Equilibrium Ratios

from Nomograms of Improved Accuracy," Journal of Chemical Engineering

Data, vol. 5, No. 3, July 1960, p. 251-259.

J.M. Lenoir, "Predict K Values at Low Temperatures, part 1," Hydrocarbon

Processing, p. 167, September 1969.

J.M. Lenoir, "Predict K Values at Low Temperatures, part 2," Hydrocarbon

Processing, p. 121, October 1969.

Fugacity Model

The Chao-Seader model calculates pure component fugacity coefficient, for

liquids. It is used in the CHAO-SEA property method. This is an empirical

model with the Curl-Pitzer form. The general form of the model is:

Where:

=

Name/Element Limit

TC Tci — — 5.0 2000.0 TEMPERATURE

PC pci — — 105 108 PRESSURE

OMEGA ωi — — -0.5 2.0 —

References

K.C. Chao and J.D. Seader, "A General Correlation of Vapor-Liquid Equilibria

in Hydrocarbon Mixtures," AIChE J., Vol. 7, (1961), p. 598.

Fugacity Model

The Grayson-Streed model calculates pure component fugacity coefficients for

liquids, and is used in the GRAYSON/GRAYSON2 property methods. It is an

empirical model with the Curl-Pitzer form. The general form of the model is:

Where:

Name/Element Limit

TC Tci — — 5.0 2000.0 TEMPERATURE

5 8

PC pci — — 10 10 PRESSURE

OMEGA ωi — — -0.5 2.0 —

References

H.G. Grayson and C.W. Streed, Paper 20-PO7, Sixth World Petroleum

Conference, Frankfurt, June 1963.

The Kent-Eisenberg model calculates liquid mixture component fugacity

coefficients and liquid enthalpy for the AMINES property method.

The chemical equilibria in H2S + CO2 + amine systems are described using

these chemical reactions:

Where:

R' = Alcohol substituted alkyl groups

The equilibrium constants are given by:

balance equations. This obtains the mole fractions of free H2S and CO2 in

solution. The equilibrium partial pressures of H2S and CO2 are related to the

respective free concentrations by Henry's constants:

The apparent fugacities and partial molar enthalpies, Gibbs energies and

entropies of H2S and CO2 are calculated by standard thermodynamic

relationships. The chemical reactions are always considered.

The values of the coefficients for the seven equilibrium constants (A1i, ... A5i)

and for the two Henry's constants B1i and B2i are built into the Aspen Physical

Property System. The coefficients for the equilibrium constants were

determined by regression. All available data for the four amines were used:

monoethanolamine, diethanolamine, disopropanolamine and diglycolamine.

You are not required to enter any parameters for this model.

References

R.L. Kent and B. Eisenberg, Hydrocarbon Processing, (February 1976),

pp. 87-92.

The Maxwell-Bonnell model calculates vapor pressure using the Maxwell-

Bonnell vapor pressure correlation for all hydrocarbon pseudo-components as

a function of temperature. This is an empirical correlation based on API

procedure 5A1.15, 5A1.13. This model is used in property method MXBONNEL

for calculating vapor pressure and liquid fugacity coefficients (K-values).

References

API procedure 5A1.15 and 5A1.13.

The vapor pressure of a solid can be calculated using the Antoine equation.

Parameters for some components are available for the extended Antoine

equation from the Aspen Physical Property System pure component databank.

This equation can be used whenever the parameter PSANT is available.

The equation for the solid Antoine vapor pressure model is:

Parameter Symbol Default MDS Lower Limit Upper Units

Name/ Limit

Element

PSANT/1 C1i — x — — PRESSURE,

TEMPERATURE

PSANT/2 C2i — x — — TEMPERATURE

PSANT/3 C3i 0 x — — TEMPERATURE

PSANT/4 C4i 0 x — — TEMPERATURE

PSANT/5 C5i 1000 x — — TEMPERATURE

DIPPR/Watson/PPDS/IK-CAPE

Heat of Vaporization Model

The Aspen Physical Property System has several submodels for calculating

pure component heat of vaporization. It uses parameter THRSWT/4 to

determine which submodel is used. See Pure Component Temperature-

Dependent Properties for details.

If THRSWT/4 is Then this equation is used

0 Watson

106 DIPPR

301 PPDS

401 IK-CAPE

505 NIST TDE Watson equation

The DIPPR equation is used to calculate heat of vaporization when THRSWT/4

is set to 106. (Other DIPPR equations may sometimes be used. See Pure

Component Temperature-Dependent Properties for details.)

The equation for the DIPPR heat of vaporization model is:

Where:

Tri = T / Tci

temperature units.

using the slope at the temperature bound, except that ΔvapHi* is zero for

.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

DHVLDP/1 C1i — x — — MOLE-ENTHALPY

DHVLDP/2, ..., 5 C2i, ..., C5i 0 x — — —

DHVLDP/6 C6i 0 x — — TEMPERATURE

DHVLDP/7 C7i 1000 x — — TEMPERATURE

TC Tci — — 5.0 2000.0 TEMPERATURE

Watson Heat of Vaporization Equation

The Watson equation is used to calculate heat of vaporization when

THRSWT/4 is set to 0. See Pure Component Temperature-Dependent

Properties for details.

The equation for the Watson model is:

Where:

temperature bound, using the slope at the temperature bound.

Parameter Symbol Default Lower Upper Units

Name/Element Limit Limit

TC Tci — 5.0 2000.0 TEMPERATURE

4 8

DHVLWT/1 ΔvapHi*(T1) — 5x10 5x10 MOLE-ENTHALPY

DHVLWT/3 ai 0.38 -2.0 2.0 —

DHVLWT/4 bi 0 -2.0 2.0 —

DHVLWT/5 Tmin 0 0.0 1500.0 TEMPERATURE

The PPDS equation is used to calculate heat of vaporization when THRSWT/4

is set to 301. See Pure Component Temperature-Dependent Properties for

details.

The equation for the PPDS model is:

using the slope at the temperature bound.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

TC Tci — 5.0 2000.0 TEMPERATURE

DHVLDS/1 C1i — — — — —

DHVLDS/2 C2i 0 — — — —

DHVLDS/3 C3i 0 — — — —

DHVLDS/4 C4i 0 — — — —

DHVLDS/5 C5i 0 — — — —

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

DHVLDS/6 C6i 0 — — TEMPERATURE

DHVLDS/7 C7i 1000 — — TEMPERATURE

The IK-CAPE equation is used to calculate heat of vaporization when

THRSWT/4 is set to 401. See Pure Component Temperature-Dependent

Properties for details.

The equation for the IK-CAPE model is:

using the slope at the temperature bound

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

DHVLPO/1 C1i — X — — MOLE-

ENTHALPY

DHVLPO/2, ..., 10C2i, ..., C10i 0 X — — MOLE-

ENTHALPY

TEMPERATURE

DHVLPO/11 C11i 0 X — — TEMPERATURE

DHVLPO/12 C12i 1000 X — — TEMPERATURE

Equation

The NIST TDE Watson equation is used to calculate heat of vaporization when

THRSWT/4 is set to 505. See Pure Component Temperature-Dependent

Properties for details.

The equation is:

using the slope at the temperature bound

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

DHVLTDEW/1 C1i — X — — —

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

DHVLTDEW/2, 3, C2i, C3i, C4i 0 X — — —

4

DHVLTDEW/5 Tci — X — — TEMPERATURE

DHVLTDEW/6 nTerms 4 X — — —

DHVLTDEW/7 Tlower 0 X — — TEMPERATURE

DHVLTDEW/8 Tupper 1000 X — — TEMPERATURE

Clausius-Clapeyron Equation

The Aspen Physical Property System can calculate heat of vaporization using

the Clausius Clapeyron equation:

Where:

= Slope of the vapor pressure curve calculated from the Extended

Antoine equation

equation of state

Vi*,l = Liquid molar volume calculated from the Rackett equation

For parameter requirements, see Extended Antoine/Wagner, the Rackett

model, and Redlich Kwong.

Models

The Aspen Physical Property System has the following built-in molar volume

and density models available. This section describes the molar volume and

density models.

Model Type

API Liquid Volume Liquid volume

Brelvi-O'Connell Partial molar liquid

volume of gases

Clarke Aqueous Electrolyte Volume Liquid volume

COSTALD Liquid Volume Liquid volume

Debye-Hückel Volume Electrolyte liquid volume

Liquid Constant Molar Volume Model Liquid volume

Rackett/DIPPR/PPDS/IK-CAPE Liquid Molar Liquid volume/liquid

Volume density

Model Type

Rackett/Campbell-Thodos Mixture Liquid Liquid volume

Volume

Modified Rackett Liquid volume

Aspen/DIPPR/IK-CAPE Solids Volume Solid volume

Liquid Volume Quadratic Mixing Rule Liquid volume

This model calculates liquid molar volume for a mixture, using the API

procedure and the Rackett model. Ideal mixing is assumed:

Where:

xp = Mole fraction of pseudocomponents

xr = Mole fraction of real components

For pseudocomponents, the API procedure is used:

Where:

fcn = A correlation based on API Figure 6A3.5 (API Technical Data Book,

Petroleum Refining, 4th edition)

At high density, the Ritter equation is used (adapted from Ritter, Lenoir, and

Schweppe, Petrol. Refiner 37 [11] 225 (1958)):

Rankine, T is the temperature of the system in Rankine, and the mass volume

is produced in units of cubic feet per pound-mass.

For real components, the mixture Rackett model is used:

temperature units.

See the Rackett model for descriptions.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

TB Tb — — 4.0 2000.0 TEMPERATURE

API API — — -60.0 500.0 —

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

TC Tc — — 5.0 2000.0 TEMPERATURE

5 8

PC pc — — 10 10 PRESSURE

RA

RKTZRA Z ZC — 0.1 0.5 —

Brelvi-O'Connell

The Brelvi-O'Connell model calculates partial molar volume of a supercritical

component i at infinite dilution in pure solvent A. Partial molar volume at

infinite dilution is required to compute the effect of pressure on Henry's

constant. (See Henry's Constant.)

The general form of the Brelvi-O'Connell model is:

Where:

i = Solute or dissolved-gas component

A = Solvent component

The liquid molar volume of solvent is obtained from the Rackett model:

temperature units.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

TC TcA — — 5.0 2000.0 TEMPERATURE

5 8

PC pcA — — 10 10 PRESSURE

RKTZRA ZARA ZC x 0.1 1.0 —

VLBROC/1 ViBO VC x -1.0 1.0 MOLE-VOLUME

VLBROC/2 — 0 x -0.1 0.1 TEMPERATURE

References

S.W. Brelvi and J.P. O'Connell, AIChE J., Vol. 18, (1972), p. 1239.

S.W. Brelvi and J.P. O'Connell, AIChE J., Vol. 21, (1975), p. 157.

The Clarke model calculates liquid molar volume for electrolytes solutions.

The model is applicable to mixed solvents and is based on:

• Molar volume of molecular solvents (equation 2)

• The relationship between the partial molar volume of an electrolyte and its

mole fraction in the solvent (equation 4)

All quantities are expressed in terms of apparent components.

If option code 1 is set to 1, the liquid volume quadratic mixing rule is used

instead. The default option uses this equation to calculate the liquid molar

volume for electrolyte solutions:

(1)

Where:

Vml = Liquid molar volume for electrolyte solutions.

Vsl = Liquid molar volume for solvent mixtures.

Vel = Liquid molar volume for electrolytes.

For molecular solvents, the liquid molar volume is calculated by:

(2)

Where:

xw = Mole fraction of water

Vw* = Molar volume of water from the steam table.

xnws = Sum of the mole fractions of all non-water

solvents.

Vnwsl = Liquid molar volume for the mixture of all non-

water solvents. It is calculated using the

Rackett equation.

For electrolytes:

(3)

(4)

(5)

Where:

xca = Apparent mole fraction of electrolyte ca

Vca = Liquid molar volume for electrolyte ca

The mole fractions xca are reconstituted arbitrarily from the true ionic

concentrations, even if you use the apparent component approach. This

technique is explained in Electrolyte Calculation in Physical Property Methods.

The result is that electrolytes are generated from all possible combinations of

ions in solution. The following equation is consistently applied to determine

the amounts of each possible apparent electrolyte nca:

(6)

Where:

nca = Number of moles of apparent electrolyte ca

zc = Charge of c

zfactor = zc if c and a have the same number of

charges; otherwise 1.

nc = Number of moles of cation c

na = Number of moles of anion a

For example: given an aqueous solution of Ca2+, Na+, SO42-, Cl- four

electrolytes are found: CaCl2, Na2SO4, CaSO4, and NaCl. The Clarke

parameters of all four electrolytes are used. You can rely on the default,

which calculates the Clarke parameters from ionic parameters. Otherwise, you

must enter parameters for any electrolytes that may not exist in the

components list. If you do not want to use the default, the first step in using

the Clarke model is to add any needed components for electrolytes not in the

components list.

The true molar volume is obtained from the apparent molar volume:

(7)

Where:

Vml,t = Liquid volume per number of true species

Vml,a = Liquid volume per number of apparent species, Vml

of equation 1

na = Number of apparent species

t

n = Number of true species

The apparent molar volume is calculated as explained in the preceding

subsection.

Temperature Dependence

The temperature dependence of the molar volume of the solution is

approximately equal to the temperature dependence of the molar volume of

the solvent mixture:

(8)

Parameter Applicable Symbol Default Units

Name/Element Components

VLCLK/1 Cation-Anion † MOLE-VOLUME

VLBROC is missing, the default value of -0.12x10-2 is used.

See also Rackett/Campbell-Thodos Mixture Liquid Volume for additional

parameters used in the Rackett equation.

Reference

C.C. Chen, private communication.

The equation for the COSTALD liquid volume model is:

Where:

δ

VmR,0 and VmR, are functions or Tr for

Tr = 0.95 and the vapor density at Tr = 1.05. This model can be used to

calculate saturated and compressed liquid molar volume. The compressed

liquid molar volume is calculated using the Tait equation:

Where B and C are functions of T, ω, Tc, Pc and Psat is the saturated pressure

at T.

temperature units.

Mixing Rules:

Where:

correlation for water when this model is used. Changing the VSTCTD and

OMGCTD parameters for water will not affect the results of the special

correlation.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

TC Tci — — 5.0 2000.0 TEMPERATURE

*,CTD

VSTCTD Vr VC X 0.001 3.5 MOLE-VOLUME

OMGCTD ωr OMEGA X -0.5 2.0 —

References

R.W. Hankinson and G.H. Thomson, AIChE J., Vol. 25, (1979), p. 653.

G.H. Thomson, K.R. Brobst, and R.W. Hankinson, AIChE J., Vol. 28, (1982),

p. 4, p. 671.

Debye-Hückel Volume

The Debye-Hückel model calculates liquid molar volume for aqueous

electrolyte solutions.

The equation for the Debye-Hückel volume model is:

Where:

∞

Vk is the molar volume for water and is calculated from the ASME steam

table.

Vk is calculated from the Debye-Hückel limiting law for ionic species. It is

assumed to be the infinite dilution partial volume for molecular solutes.

Where:

∞ = Partial molar ionic volume at infinite dilution

Vk

zk = Charge number of ion k

Av = Debye-Hückel constant for volume

b = 1.2

I =

the ionic strength, with

mk = Molarity of ion k

Av is computed as follows:

Where:

coefficients (Pitzer, 1979)

of pressure and temperature (Bradley and

Pitzer, 1979)

Components

VLBROC Ions, molecular Solutes Vk∞ 0 MOLE-VOLUME

References

D. J. Bradley, K. S. Pitzer, "Thermodynamics of Electrolytes," J. Phys. Chem.,

83 (12), 1599 (1979).

H.C. Helgeson and D.H. Kirkham, "Theoretical prediction of the

thermodynamic behavior of aqueous electrolytes at high pressure and

temperature. I. Thermodynamic/electrostatic properties of the solvent", Am.

J. Sci., 274, 1089 (1974).

K.S. Pitzer, "Theory: Ion Interaction Approach," Activity Coefficients in

Electrolyte Solutions, Pytkowicz, R. ed., Vol. I, (CRC Press Inc., Boca Raton,

Florida, 1979).

This model, VL0CONS, uses a constant value entered by the user as the pure

component liquid molar volume. It is not a function of temperature or

pressure. This is used with the solids handling property method for modeling

nonconventional solids.

Parameter Name Default MDS Units

VLCONS 1 x MOLE-VOLUME

Rackett/DIPPR/PPDS/IK-CAPE Liquid

Molar Volume

The Aspen Physical Property System has several submodels for calculating

liquid molar volume. It uses parameter THRSWT/2 to determine which

submodel is used. See Pure Component Temperature-Dependent Properties

for details.

If THRSWT/2 is This equation is used And this parameter is used

0 Rackett RKTZRA

100-116 DIPPR DNLDIP

301 PPDS DNLPDS

401 IK-CAPE VLPO

503 NIST ThermoML DNLTMLPO

Polynomial

504 NIST TDE expansion DNLEXSAT

514 NIST TDE Rackett DNLRACK

515 NIST COSTALD DNLCOSTD

For liquid molar volume of mixtures, the Rackett mixture equation is always

used by default. This is not necessarily consistent with the pure component

molar volume or density. If you need consistency, select route VLMX26 on the

Properties | Property Methods form. This route calculates mixture molar

volume from the mole-fraction average of pure component molar volumes.

Many of these equations calculate density first, and return calculate liquid

molar volume based on that density:

DIPPR

DIPPR equation 105 is the default DIPPR equation for most substances:

DIPPR equation 116 is the default equation for water.

τ = 1 - T / Tc

Other DIPPR equations, such as equation 100, may be used for some

substances. Check the value of THRSWT/2 to determine the equation used.

See Pure Component Temperature-Dependent Properties for details about

DIPPR equations.

temperature bounds.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

DNLDIP/1 C1i — x — — MOLE-DENSITY †

DNLDIP/2 C2i 0 x — — †

DNLDIP/3 C3i Tci † x — — TEMPERATURE †

DNLDIP/4 C4i 0 x — — †

DNLDIP/5 C5i 0 x — — †

DNLDIP/6 C6i 0 x — — TEMPERATURE

DNLDIP/7 C7i 1000 x — — TEMPERATURE

† For equation 116, the units are MOLE-DENSITY for parameters DNLDIP/1

through DNLDIP/5 and the default for DNLDIP/3 is 0. For equation 105,

DNLDIP/5 is not used, and absolute temperature units are assumed for

DNLDIP/3.

PPDS

The PPDS equation is:

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

MW Mi — — 1.0 5000.0 —

VC Vci — — 0.001 3.5 MOLE-VOLUME

TC Tci — — 5.0 2000.0 TEMPERATURE

DNLPDS/1 C1i — — — — MASS-DENSITY

DNLPDS/2 C2i 0 — — — MASS-DENSITY

DNLPDS/3 C3i 0 — — — MASS-DENSITY

DNLPDS/4 C4i 0 — — — MASS-DENSITY

DNLPDS/5 C5i 0 x — — TEMPERATURE

DNLPDS/6 C6i 1000 x — — TEMPERATURE

IK-CAPE

The IK-CAPE equation is:

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

VLPO/1 C1i — X — — MOLE-

VOLUME

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

VLPO/2, ..., 10 C2i, ..., C10i 0 X — — MOLE-

VOLUME

TEMPERATURE

VLPO/11 C11i 0 X — — TEMPERATURE

VLPO/12 C12i 1000 X — — TEMPERATURE

This equation can be used when parameter DNLTMLPO is available.

Name/Element Limit Limit

DNLTMLPO/1 C1i — X — — MOLE-

DENSITY

DNLTMLPO/2, 3, C2i, C3i, C4i 0 X — — MOLE-

4 DENSITY

TEMPERATURE

DNLTMLPO/5 nTerms 4 X — — —

DNLTMLPO/6 0 X — — TEMPERATURE

Rackett

The Rackett equation is:

Where:

Tr = T / Tci

temperature units.

Parameter Symbol Default MDS Lower Upper Units

Name/ Limit Limit

Element

TC Tci — — 5.0 2000.0 TEMPERATURE

5 8

PC pci — — 10 10 PRESSURE

RKTZRA Zi*,RA ZC x 0.1 1.0 —

This equation can be used when the parameter DNLRACK is available.

Linear extrapolation of Vi*,l versus T occurs outside of temperature bounds.

Parameter Symbol Default MDS Lower Upper Units

Name/ Limit Limit

Element

DNLRACK/1 Zc — x — — —

DNLRACK/2 n 2/7 x — — —

DNLRACK/3 Tci — x — — TEMPERATURE

DNLRACK/4 pci 0 x — — PRESSURE

DNLRACK/5 Tlower 0 x — — TEMPERATURE

DNLRACK/6 Tupper 1000 x — — TEMPERATURE

This equation can be used when the parameter DNLCOSTD is available.

Parameter Symbol Default MDS Lower Upper Units

Name/ Limit Limit

Element

DNLCOSTD/1 Voi — x — — VOLUME

DNLCOSTD/2 Ω 0 x — — —

DNLCOSTD/4 Tlower 0 x — — TEMPERATURE

DNLCOSTD/5 Tupper 1000 x — — TEMPERATURE

This equation can be used when the parameter DNLEXSAT is available.

Parameter Symbol Default MDS Lower Upper Units

Name/ Limit Limit

Element

DNLEXSAT/1 ρci — x — — MOLE-

DENSITY

DNLEXSAT/2 C1i — x — — MOLE-

DENSITY

DNLEXSAT/3, C2i, ..., C6i 0 x — — MOLE-

..., DNLEXSAT/7 DENSITY

DNLEXSAT/8 Tci — x — — TEMPERATURE

DNLEXSAT/9 nTerms 6 x — — —

DNLEXSAT/10 Tlower 0 x — — TEMPERATURE

DNLEXSAT/11 Tupper 1000 x — — TEMPERATURE

References

H.G. Rackett, J.Chem. Eng. Data., Vol. 15, (1970), p. 514.

C.F. Spencer and R.P. Danner, J. Chem. Eng. Data, Vol. 17, (1972), p. 236.

Volume

The Rackett equation calculates liquid molar volume for all activity coefficient

based and petroleum tuned equation of state based property methods. In the

last category of property methods, the equation is used in conjunction with

the API model. The API model is used for pseudocomponents, while the

Rackett model is used for real components. (See API Liquid Volume .)

Campbell-Thodos is a variation on the Rackett model which allows the

compressibility term Zi*,RA to vary with temperature.

Rackett

The equation for the Rackett model is:

Where:

Tc =

ZmRA =

Vcm =

Tr = T / Tc

temperature units.

Parameter Symbol Default MDS Lower Upper Units

Name/ Limit Limit

Element

TC Tci — — 5.0 2000.0 TEMPERATURE

PC pci — — 105 108 PRESSURE

VCRKT Vci VC x 0.001 3.5 MOLE-

VOLUME

RKTZRA Zi*,RA ZC x 0.1 1.0 —

RKTKIJ kij x -5.0 5.0 —

Campbell-Thodos

The Campbell-Thodos model uses the same equation and parameters as the

Rackett model, above, except that ZmRAis allowed to vary with temperature:

ZmRA =

parameters. Tmin and Tmax define the temperature range where the

equation is applicable.

Parameter Symbol Default MDS Lower Upper Units

Name/ Limit Limit

Element

RACKET/1 R*Tci/Pci R*Tci/Pci — — — MOLE-

VOLUME

RACKET/2 Zi*,RA RKTZRA x 0.1 1.0 —

RACKET/3 di 0 x 0 0.11 —

RACKET/4 Tmin 0 x — — TEMPERATURE

RACKET/5 Tmax 1000 x — — TEMPERATURE

than 0.11. The default value, 2/7, indicates that the standard Rackett

equation should be used. When Campbell-Thodos is not used, RACKET/3

should be kept at its default value of 2/7 for all components.

References

H.G. Rackett, J.Chem, Eng. Data., Vol. 15, (1970), p. 514.

C.F. Spencer and R.P. Danner, J. Chem. Eng. Data, Vol. 17, (1972), p. 236.

Modified Rackett Liquid Molar Volume

The Modified Rackett equation improves the accuracy of liquid mixture molar

volume calculation by introducing additional parameters to compute the pure

component parameter RKTZRA and the binary parameter kij.

The equation for the Modified Rackett model is:

Where:

Tc =

kij =

ZmRA =

Zi*,RA =

Vcm =

Tr = T / Tc

temperature units.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

MRKZRA/1 ai RKTZRA x 0.1 0.5 —

MRKZRA/2 bi 0 x — — —

MRKZRA/3 ci 0 x — — —

MRKKIJ/1 Aij x — — —

MRKKIJ/2 Bij 0 x — — —

MRKKIJ/3 Cij 0 x — — —

References

H.G. Rackett, J.Chem, Eng. Data., Vol. 15, (1970), p. 514.

C.F. Spencer and R.P. Danner, J. Chem. Eng. Data, Vol. 17, (1972), p. 236.

Aspen/DIPPR/IK-CAPE Solid Molar Volume

The Aspen Physical Property System has several submodels for calculating

solid molar volume. It uses parameter THRSWT/1 to determine which

submodel is used. See Pure Component Temperature-Dependent Properties

for details.

If THRSWT/1 is This equation is used And this parameter is

used

0 Aspen VSPOLY

100 DIPPR DNSDIP

401 IK-CAPE VSPO

503 NIST ThermoML DNSTMLPO

polynomial

Aspen Polynomial

The equation for the Aspen solids volume polynomial is:

Parameter Applicable Symbol MDS Default Units

Name Components

VSPOLY/1 Salts, CI solids C1i x — MOLE-VOLUME

TEMPERATURE

VSPOLY/2, ..., 5 Salts, CI solids C2i, ..., C5i x 0 MOLE-VOLUME

TEMPERATURE

VSPOLY/6 Salts, CI solids C6i x 0 MOLE-VOLUME

TEMPERATURE

VSPOLY/7 Salts, CI solids C7i x 1000 MOLE-VOLUME

TEMPERATURE

IK-CAPE Equation

The IK-CAPE equation is:

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

VSPO/1 C1i — X — — MOLE-

VOLUME

VSPO/2, ..., 10 C2i, ..., C10i 0 X — — MOLE-

VOLUME

TEMPERATURE

VSPO/11 C11i 0 X — — TEMPERATURE

VSPO/12 C12i 1000 X — — TEMPERATURE

DIPPR

The DIPPR equation is:

Vi*,s = 1 / ρi*,s

(Other DIPPR equations may sometimes be used. See Pure Component

Temperature-Dependent Properties for details.)

The model returns solid molar volume for pure components.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

DNSDIP/1 C1i — x — — MOLE-

DENSITY

DNSDIP/2, ..., 5 C2i, ..., C5i 0 x — — MOLE-

DENSITY,

TEMPERATURE

DNSDIP/6 C6i 0 x — — TEMPERATURE

DNSDIP/7 C7i 1000 x — — TEMPERATURE

Vi*,s = 1 / ρi*,s

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

DNSTMLPO/1 C1i — x — — MOLE-

DENSITY

DNSTMLPO/2,...,8 C2i, ..., C8i 0 x — — MOLE-

DENSITY,

TEMPERATURE

DNSTMLPO/9 nTerms 8 x — — —

DNSTMLPO/10 Tlower 0 x — — TEMPERATURE

DNSTMLPO/11 Tupper 1000 x — — TEMPERATURE

With i and j being components, the liquid volume quadratic mixing rule is:

Option Codes

Option Code Value Descriptions

1 0 Use normal pure component liquid volume model for all

components (default)

1 Use steam tables for water

2 0 Use mole basis composition (default)

1 Use mass basis composition

Parameter

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

VLQKIJ Kij - x - - —

This model is not part of any property method. To use it, you will need to

define a property method on the Properties | Property Methods form.

Specify the route VLMXQUAD for VLMX on the Routes sheet of this form, or

the model VL2QUAD for VLMX on the Models sheet.

The Aspen Physical Property System has five built-in heat capacity models.

This section describes the heat capacity models available.

Model Type

Aqueous Infinite Dilution Heat Capacity Electrolyte liquid

Polynomial

Criss-Cobble Aqueous Infinite Dilution Electrolyte liquid

Ionic Heat Capacity

DIPPR/PPDS/IK-CAPE Liquid Heat Capacity Liquid

Aspen/DIPPR/Barin/PPDS/IK-CAPE Ideal Ideal gas

Gas Heat Capacity

Aspen/DIPPR/Barin/IK-CAPE Solid Heat Solid

Capacity

The aqueous phase infinite dilution enthalpies, entropies, and Gibbs energies

are calculated from the heat capacity polynomial. The values are used in the

calculation of aqueous and mixed solvent properties of electrolyte solutions:

versus T is linearly extrapolated using the slope at C7i for T < C7i

versus T is linearly extrapolated using the slope at C8i for T < C8i

Parameter Applicable Symbol Default Units

Name/Element Components

CPAQ0/1 Ions, molecular solutes C1i — TEMPERATURE and

HEAT CAPACITY

CPAQ0/2,…,6 Ions, molecular solutes C2i, ..., C6i 0 TEMPERATURE and

HEAT CAPACITY

CPAQ0/7 Ions, molecular solutes C7i 0 TEMPERATURE

CPAQ0/8 Ions, molecular solutes C8i 1000 TEMPERATURE

assumed for C1i through C6i . Otherwise, user input units for temperature are

used. The temperature limits are always interpreted in user input units.

Heat Capacity

The Criss-Cobble correlation for aqueous infinite dilution ionic heat capacity is

used if no parameters are available for the aqueous infinite dilution heat

capacity polynomial. From the calculated heat capacity, the thermodynamic

properties entropy, enthalpy and Gibbs energy at infinte dilution in water are

derived:

Name Components

IONTYP Ions Ion Type 0 —

SO25C Anions MOLE-ENTROPY

Cations MOLE-ENTROPY

The Aspen Physical Property System has several submodels for calculating

liquid heat capacity. It uses parameter THRSWT/6 to determine which

submodel is used. See Pure Component Temperature-Dependent Properties

for details.

If THRSWT/6 is This equation is used And this parameter is used

100 DIPPR CPLDIP

200 Barin CPLXP1, CPLXP2

301 PPDS CPLPDS

401 IK-CAPE heat capacity CPLPO

polynomial

403 IK-CAPE liquid heat CPLIKC

capacity

If THRSWT/6 is This equation is used And this parameter is used

503 NIST ThermoML CPLTMLPO

polynomial

506 NIST TDE equation CPLTDECS

component liquid heat capacity and pure component liquid enthalpy. To use

this model, two conditions must exist:

• One of the parameters for calculating heat capacity (see table below) is

available.

• The component is not supercritical (HENRY-COMP).

The model uses a specific method (see Methods in Property Calculation

Methods and Routes):

Where

= Reference enthalpy calculated at Tref

= Enthalpy of vaporization

different value for the reference temperature. This is useful when you want to

use this model for very light components or for components that are solids at

298.15K.

Activate this model by specifying the route DHL09 for the property DHL on

the Properties Property Methods Routes sheet. For equation of state property

method, you must also modify the route for the property DHLMX to use a

route with method 2 or 3, instead of method 1. For example, you can use the

route DHLMX00 or DHLMX30. You must ascertain that the route for DHLMX

that you select contains the appropriate vapor phase model and heat of

mixing calculations. Click the View button on the form to see details of the

route.

Optionally, you can specify that this model is used for only certain

components. The properties for the remaining components are then

calculated by the standard model. Use the parameter COMPHL to specify the

components for which this model is used. By default, all components with the

CPLDIP or CPLIKC parameters use this model.

DIPPR Liquid Heat Capacity

The DIPPR equation is used to calculate liquid heat capacity when parameter

THRSWT/6 is 100.

The DIPPR equation is:

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

CPLDIP/1 C1i — x — — MOLE-HEAT-

CAPACITY,

TEMPERATURE

CPLDIP/2, ..., 5 C2i, ..., C5i 0 x — — MOLE-HEAT-

CAPACITY,

TEMPERATURE

CPLDIP/6 C6i 0 x — — TEMPERATURE

CPLDIP/7 C7i 1000 x — — TEMPERATURE

TREFHL Tref 298.15 — — — TEMPERATURE

COMPHL — — — — — —

To specify that the model is used for a component, enter a value of 1.0 for

COMPHL.

(Other DIPPR equations may sometimes be used. See Pure Component

Temperature-Dependent Properties for details.)

The PPDS equation is used to calculate liquid heat capacity when parameter

THRSWT/6 is 301.

The PPDS equation is:

Linear extrapolation occurs for Cp*,l versus T outside of bounds.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

CPLPDS/1 C1i — — — — —

CPLPDS/2 C2i 0 — — — —

CPLPDS/3 C3i 0 — — — —

CPLPDS/4 C4i 0 — — — —

CPLPDS/5 C5i 0 — — — —

CPLPDS/6 C6i 0 — — — —

CPLPDS/7 C7i 0 x — — TEMPERATURE

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

CPLPDS/8 C8i 1000 x — — TEMPERATURE

Two IK-CAPE equations can be used to calculate liquid heat capacity. Linear

extrapolation occurs for Cp*,l versus T outside of bounds for either equation.

When THRSWT/6 is 403, the IK-CAPE liquid heat capacity equation is used.

The equation is:

Name/Element Limit Limit

CPLIKC/1 C1i — x — — MOLE-HEAT-

T CAPACITY

CPLIKC/2,...,4 C2i, ..., C4i 0 x — — MOLE-HEAT-

CAPACITY,

TEMPERATURE

CPLIKC/5 C5i 0 x — — MOLE-HEAT-

CAPACITY,

TEMPERATURE †

CPLIKC/6 C6i 0 x — — TEMPERATURE

CPLIKC/7 C7i 1000 x — — TEMPERATURE

† If C5i is non-zero, absolute temperature units are assumed for C2i through

C5i. Otherwise, user input units for temperature are used. The temperature

limits are always interpreted in user input units.

When THRSWT/6 is 401, the IK-CAPE heat capacity polynomial is used.The

equation is:

Name/Element Limit Limit

CPLPO/1 C1i — X — — MOLE-CAPACITY

CPLPO/2,…,10 C2i, ..., C10i 0 X — — MOLE-CAPACITY

TEMPERATURE

CPLPO/11 C11i 0 X — — TEMPERATURE

CPLPO/12 C12i 1000 X — — TEMPERATURE

THRSWT parameters.

NIST Liquid Heat Capacity

Two NIST equations can be used to calculate liquid heat capacity. Linear

extrapolation occurs for Cp*,l versus T outside of bounds for either equation.

When THRSWT/6 is 503, the ThermoML polynomial is used to calculate liquid

heat capacity:

Name/Element Limit Limit

CPLTMLPO/1 C1i — X — — J/K^2/mol

CPLTMLPO/2,…,5 C2i, ..., C5i 0 X — — J/K^2/mol

CPLTMLPO/6 nTerms 5 X — — —

CPLTMLPO/7 Tlower 0 X — — TEMPERATURE

CPLTMLPO/8 Tupper 1000 X — — TEMPERATURE

When THRSWT/6 is 506, the TDE equation is used to calculate liquid heat

capacity:

Name/Element Limit Limit

CPLTDECS/1 C1i — X — — MOLE-HEAT-

CAPACITY

CPLTDECS/2,…,4 C2i, ..., C4i 0 X — — MOLE-HEAT-

CAPACITY

CPLTDECS/5 B 0 X — — MOLE-HEAT-

CAPACITY

CPLTDECS/6 Tci — X — — TEMPERATURE

CPLTDECS/7 nTerms 4 X — — —

CPLTDECS/8 Tlower 0 X — — TEMPERATURE

CPLTDECS/9 Tupper 1000 X — — TEMPERATURE

THRSWT parameters.

Aspen/DIPPR/Barin/PPDS/IK-CAPE Ideal

Gas Heat Capacity

The Aspen Physical Property System has several submodels for calculating

ideal gas heat capacity. It uses parameter THRSWT/7 to determine which

submodel is used. See Pure Component Temperature-Dependent Properties

for details.

If THRSWT/7 is This equation is used And this parameter is

used

0 Ideal gas heat capacity CPIG

polynomial

107 DIPPR CPIGDP

200 Barin CPIXP1, CPIXP2, CPIXP3

301 PPDS CPIGDS

401 IK-CAPE heat capacity CPIGPO

polynomial

503 NIST ThermoML CPITMLPO

polynomial

513 NIST Aly-Lee CPIALEE

These equations are also used to calculate ideal gas enthalpies, entropies,

and Gibbs energies.

The ideal gas heat capacity polynomial is available for components stored in

ASPENPCD, AQUEOUS, and SOLIDS databanks. This model is also used in

PCES.

Parameter Symbol Default MDS Lower Upper Units

Name/ Limit Limit

Element

CPIG/1 C1i — — — — MOLE-HEAT-CAPACITY,

TEMPERATURE

CPIG/2, ..., 6 C2i, ..., C6i 0 — — — MOLE-HEAT-CAPACITY,

TEMPERATURE

CPIG/7 C7i 0 — — — TEMPERATURE

CPIG/8 C8i 1000 — — — TEMPERATURE

CPIG/9, 10, C9i, C10i, C11i — — — — MOLE-HEAT-CAPACITY,

11 TEMPERATURE †

† If C10i or C11i is non-zero, then absolute temperature units are assumed for

C9i through C11i. Otherwise, user input temperature units are used for all

parameters. User input temperature units are always used for C1i through C8i.

This equation can be used when parameter CPITMLPO is available.

Parameter Symbol Default MDS Lower Upper Units

Name/ Limit Limit

Element

CPITMLPO /1 C1i — x — — J/K^2/mol

CPITMLPO /2, C2i, ..., C6i 0 x — — J/K^2/mol

..., 6

CPITMLPO/7 nTerms 6 x — — —

CPITMLPO /8 Tlower 0 x — — TEMPERATURE

CPITMLPO /9 Tupper 1000 x — — TEMPERATURE

DIPPR

The DIPPR ideal gas heat capacity equation by Aly and Lee 1981 is:

(Other DIPPR equations may sometimes be used. See Pure Component

Temperature-Dependent Properties for details.)

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

CPIGDP/1 C1i — x — — MOLE-HEAT-

CAPACITY

CPIGDP/2 C2i 0 x — — MOLE-HEAT-

CAPACITY

CPIGDP/3 C3i 0 x — — TEMPERATURE ††

CPIGDP/4 C4i 0 x — — MOLE-HEAT-

CAPACITY

CPIGDP/5 C5i 0 x — — TEMPERATURE ††

CPIGDP/6 C6i 0 x — — TEMPERATURE

CPIGDP/7 C7i 1000 x — — TEMPERATURE

†† Absolute temperature units are assumed for C3i and C5i. The temperature

limits are always interpreted in user input units.

NIST Aly-Lee

This equation is the same as the DIPPR Aly and Lee equation above, but it

uses a different parameter set. Note that elements 6 and 7 of the CPIALEE

parameter are not used in the equation.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

CPIALEE/1 C1i — x — — MOLE-HEAT-

CAPACITY

CPIALEE/2 C2i 0 x — — MOLE-HEAT-

CAPACITY

CPIALEE/3 C3i 0 x — — TEMPERATURE ††

CPIALEE/4 C4i 0 x — — MOLE-HEAT-

CAPACITY

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

CPIALEE/5 C5i 0 x — — TEMPERATURE ††

CPIALEE/8 C6i 0 x — — TEMPERATURE

CPIALEE/9 C7i 1000 x — — TEMPERATURE

†† Absolute temperature units are assumed for C3i and C5i. The temperature

limits are always interpreted in user input units.

PPDS

The PPDS equation is:

Linear extrapolation of Cp*,ig versus T is performed outside temperature

bounds.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

CPIGDS/1 C1i — — — — TEMPERATURE

CPIGDS/2, …, 8 C2i, ..., C8i 0 — — — —

CPIGDS/9 C9i 0 — — — TEMPERATURE

CPIGDS/10 C10i 1000 — — — TEMPERATURE

The equation is:

bounds.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

CPIGPO/1 C1i — X — — MOLE-CAPACITY

CPIGPO/2,…,10 C2i, ..., C10i 0 X — — MOLE-CAPACITY

TEMPERATURE

CPIGPO/11 C11i 0 X — — TEMPERATURE

CPIGPO/12 C12i 1000 X — — TEMPERATURE

References

Data for the Ideal Gas Heat Capacity Polynomial: Reid, Prausnitz and Poling,

The Properties of Gases and Liquids, 4th ed., (New York: McGraw-Hill, 1987).

The Aspen Physical Property System combustion data bank, JANAF

Thermochemical Data, Compiled and calculated by the Thermal Research

Laboratory of Dow Chemical Company.

F. A. Aly and L. L. Lee, "Self-Consistent Equations for Calculating the Ideal

Gas Heat Capacity, Enthalpy, and Entropy, Fluid Phase Eq., Vol. 6, (1981), p.

169.

Capacity

The Aspen Physical Property System has several submodels for calculating

solid heat capacity. It uses parameter THRSWT/5 to determine which

submodel is used. See Pure Component Temperature-Dependent Properties

for details.

If THRSWT/5 is This equation is used And this parameter is

used

0 Aspen solid heat capacity CPSPO1

polynomial

100 DIPPR CPSDIP

200 Barin CPSXP1, CPSXP2, …,

CPSXP7

401 IK-CAPE heat capacity CPSPO

polynomial

503 NIST ThermoML CPSTMLPO

polynomial

The enthalpy, entropy, and Gibbs energy of solids are also calculated from

these equations:

The Aspen equation is:

Parameter Applicable Symbol MDS Default Units

Name Components

CPSPO1/1 Solids, Salts C1i x — †

CPSPO1/2, ..., 6 Solids, Salts C2i, ..., C6i x 0 †

CPSPO1/7 Solids, Salts C7i x 0 †

CPSPO1/8 Solids, Salts C8i x 1000 †

† The units are TEMPERATURE and HEAT-CAPACITY for all elements. If any of

C4i through C6i are non-zero, absolute temperature units are assumed for

elements C1i through C6i. Otherwise, user input temperature units are

assumed for all elements. The temperature limits are always interpreted in

user input units.

DIPPR

The DIPPR equation is:

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

CPSDIP/1 C1i — x — — MOLE-HEAT-

CAPACITY,

TEMPERATURE

CPSDIP/2,...,5 C2i, ..., C5i 0 x — — MOLE-HEAT-

CAPACITY,

TEMPERATURE

CPSDIP/6 C6i 0 x — — TEMPERATURE

CPSDIP/7 C7i 1000 x — — TEMPERATURE

Temperature-Dependent Properties for details.)

The equation is:

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

CPSTMLPO/1 C1i — x — — J/K^2/mol

CPSTMLPO/2,...,5C2i, ..., C5i 0 x — — J/K^2/mol

CPSTMLPO/6 nTerms 5 x — — —

CPSTMLPO/7 Tlower 0 x — — TEMPERATURE

CPSTMLPO/8 Tupper 1000 x — — TEMPERATURE

The equation is:

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

CPSPO/1 C1i — X — — MOLE-CAPACITY

CPSPO/2,…,10 C10i 0 X — — MOLE-CAPACITY

TEMPERATURE

CPSPO/11 C11i 0 X — — TEMPERATURE

CPSPO/12 C12i 1000 X — — TEMPERATURE

Solubility Correlations

The Aspen Physical Property System has three built-in solubility correlation

models. This section describes the solubility correlation models available.

Model Type

Henry's constant Gas solubility in liquid

Water solubility Water solubility in organic liquid

Hydrocarbon solubility Hydrocarbon solubility in water-rich

liquid

Henry's Constant

The Henry's constant model is used when Henry's Law is applied to calculate

K-values for dissolved gas components in a mixture. Henry's Law is available

in all activity coefficient property methods, such as the WILSON property

method. The model calculates Henry's constant for a dissolved gas component

(i) in one or more solvents (A or B):

Where:

wA =

ln HiA(T, pA*,l) =

HiA(T, P) =

obtained from the Antoine model. is obtained from the appropriate activity

coefficient model.

The Henry's constants aiA, biA, ciA, diA, and eiA are specific to a solute-solvent

pair. They can be obtained from regression of gas solubility data. The Aspen

Physical Property System has a large number of built-in Henry's constants for

many solutes in solvents. These parameters were obtained using data from

the Dortmund Databank. See Physical Property Data, Chapter 1, for details.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

VC VcA — — 0.001 3.5 MOLE-VOLUME

HENRY/1 aiA †† x — — PRESSURE,

TEMPERATURE †

HENRY/2 biA 0 x — — TEMPERATURE †

HENRY/3 ciA 0 x — — TEMPERATURE †

HENRY/4 diA 0 x — — TEMPERATURE †

HENRY/5 TL 0 x — — TEMPERATURE

HENRY/6 TH 2000 x — — TEMPERATURE

HENRY/7 eiA 0 x — — TEMPERATURE †

† If any of biA, ciA, and eiA are non-zero, absolute temperature units are

assumed for all coefficients. If biA, ciA, and eiA are all zero, the others are

interpreted in input units. The temperature limits are always interpreted in

input units.

renormalized.

Water Solubility

This model calculates solubility of water in a hydrocarbon-rich liquid phase.

The model is used automatically when you model a hydrocarbon-water

system with the free-water option. See Free-Water Immiscibility Simplification

in Free-Water and Three-Phase Calculations for details.

The expression for the liquid mole fraction of water in the ith hydrocarbon

species is:

The parameters for about 60 components are stored in the Aspen Physical

Property System pure component databank.

Parameter Symbol Default MDS Lower Upper Units

Name/ Limit Limit

Element

WATSOL/1 C1i fcn(Tbi, SGi, Mi) — -10.0 33.0 —

WATSOL/2 C2i fcn(Tbi, SGi, Mi) — -10000.0 3000.0 TEMPERATURE †

WATSOL/3 C3i 0 — -0.05 0.05 TEMPERATURE †

Parameter Symbol Default MDS Lower Upper Units

Name/ Limit Limit

Element

WATSOL/4 C4i 0 — 0.0 500 TEMPERATURE †

WATSOL/5 C5i 1000 — 4.0 1000 TEMPERATURE †

Hydrocarbon Solubility

This model calculates solubility of hydrocarbon in a water-rich liquid phase.

The model is used automatically when you model a hydrocarbon-water

system with the dirty-water option. See Free-Water Immiscibility

Simplification in Free-Water and Rigorous Three-Phase Calculations for

details.

The expression for the liquid mole fraction of the ith hydrocarbon species in

water is:

The parameters for about 40 components are stored in the Aspen Physical

Property System pure component databank.

Parameter Symbol Default MDS Lower Upper Units

Name/ Limit Limit

Element

HCSOL/1 C1i fcn(carbon — -1000.0 1000.0 —

number) †

HCSOL/2 C2i 0 — -100000.0 100000.0 TEMPERATURE ††

HCSOL/3 C3i 0 — -100.0 100.0 TEMPERATURE ††

HCSOL/4 C4i 0 — 0.0 500 TEMPERATURE

HCSOL/5 C5i 1000 — 4.0 1000 TEMPERATURE

by the method given by API Procedure 9A2.17 at 25 C.

†† Absolute temperature units are assumed for elements 2 and 3. The

temperature limits are always interpreted in user input units.

Reference

C. Tsonopoulos, Fluid Phase Equilibria, 186 (2001), 185-206.

Other Thermodynamic Property

Models

The Aspen Physical Property System has some built-in additional

thermodynamic property models that do not fit in any other category. This

section describes these models:

• Cavett Liquid Enthalpy Departure

• Barin Equations for Gibbs Energy, Enthalpy, Entropy and Heat Capacity

• Electrolyte NRTL Enthalpy

• Electrolyte NRTL Gibbs Energy

• Liquid Enthalpy from Liquid Heat Capacity Correlation

• Enthalpies Based on Different Reference States

• Helgeson Equations of State

• Quadratic Mixing Rule

Cavett

The general form for the Cavett model is:

Name/Element Limit Limit

TC Tci — — 5.0 2000.0 TEMPERATURE

PC pci — — 105 108 PRESSURE

DHLCVT ZC X 0.1 0.5 —

Entropy, and Heat Capacity

The following equations are used when parameters from the Aspen Physical

Property System inorganic databank are retrieved.

• Gibbs energy:

(1)

• Enthalpy:

(2)

• Entropy:

(3)

• Heat capacity:

(4)

α refers to an arbitrary phase which can be solid, liquid, or ideal gas. For each

phase, multiple sets of parameters from 1 to n are present to cover multiple

temperature ranges. The value of the parameter n depends on the phase.

(See tables that follow.) When the temperature is outside all these

temperature ranges, linear extrapolation of properties versus T is performed

using the slope at the end of the nearest temperature bound.

The four properties Cp, H, S, and G are interrelated as a result of the

thermodynamic relationships:

properties Cp, H, S, and G (equations 1 to 4). The parameters an,i to hn,i can

occur in more than one equation.

The Aspen Physical Property System has other models which can be used to

calculate temperature-dependent properties which the BARIN equations can

calculate. The Aspen Physical Property System uses the parameters in

THRSWT to determine which model is used. See Pure Component

Temperature-Dependent Properties for details.

If this parameter is 200 Then the BARIN equations are

used to calculate

THRSWT/3 Liquid vapor pressure

THRSWT/5 Solid heat capacity

THRSWT/6 Liquid heat capacity

THRSWT/7 Ideal gas heat capacity

Solid Phase

The parameters in range n are valid for temperature: Tn,ls < T < Tn,hs

When you specify this parameter, be sure to specify at least elements 1

through 3.

Parameter Name † Symbol Default MDS Lower Upper Units

/Element Limit Limit

CPSXPn/1 Tn,ls — x — — TEMPERATURE

CPSXPn/2 Tn,hs — x — — TEMPERATURE

CPSXPn/3 an,is — x — — ††

CPSXPn/4 bn,is 0 x — — ††

CPSXPn/5 cn,is 0 x — — ††

CPSXPn/6 dn,is 0 x — — ††

Parameter Name † Symbol Default MDS Lower Upper Units

/Element Limit Limit

CPSXPn/7 en,is 0 x — — ††

CPSXPn/8 fn,is 0 x — — ††

CPSXPn/9 gn,is 0 x — — ††

CPSXPn/10 hn,is 0 x — — ††

temperature range. CPSXP2 vector stores solid parameters for the second

temperature range, and so on.

†† TEMPERATURE, ENTHALPY, ENTROPY

Liquid Phase

The parameters in range n are valid for temperature: Tn,ll < T < Tn,hl

When you specify this parameter, be sure to specify at least elements 1

through 3.

Parameter Name † Symbol Default MDS Lower Upper Units

/Element Limit Limit

CPLXPn/1 Tn,ll — x — — TEMPERATURE

CPLXPn/2 Tn,hl — x — — TEMPERATURE

l

CPLXPn/3 an,i — x — — ††

CPLXPn/4 bn,il 0 x — — ††

CPLXPn/5 cn,il 0 x — — ††

CPLXPn/6 dn,il 0 x — — ††

l

CPLXPn/7 en,i 0 x — — ††

CPLXPn/8 fn,il 0 x — — ††

l

CPLXPn/9 gn,i 0 x — — ††

CPLXPn/10 hn,il 0 x — — ††

range. CPLXP2 stores liquid parameters for the second temperature range.

†† TEMPERATURE, ENTHALPY, ENTROPY

The parameters in range n are valid for temperature: Tn,lig < T < Tn,hig

When you specify this parameter, be sure to specify at least elements 1

through 3.

Parameter Name † Symbol Default MDS Lower Upper Units

/Element Limit Limit

CPIXPn/1 Tn,lig — x — — TEMPERATURE

CPIXPn/2 Tn,hig — x — — TEMPERATURE

ig

CPIXPn/3 an,i — x — — ††

CPIXPn/4 bn,iig 0 x — — ††

CPIXPn/5 cn,iig 0 x — — ††

CPIXPn/6 dn,iig 0 x — — ††

ig

CPIXPn/7 en,i 0 x — — ††

Parameter Name † Symbol Default MDS Lower Upper Units

/Element Limit Limit

CPIXPn/8 fn,iig 0 x — — ††

ig

CPIXPn/9 gn,i 0 x — — ††

CPIXPn/10 hn,iig 0 x — — ††

† n is 1 through 3. CPIXP1 vector stores ideal gas parameters for the first

temperature range. CPIXP2 vector stores ideal gas parameters for the second

temperature range, and so on.

†† TEMPERATURE, ENTHALPY, ENTROPY

The equation for the electrolyte NRTL enthalpy model is:

The molar enthalpy Hm* and the molar excess enthalpy Hm*E are defined with

the asymmetrical reference state: the pure solvent water and infinite dilution

of molecular solutes and ions. (here * refers to the asymmetrical reference

state.)

Hw* is the pure water molar enthalpy, calculated from the Ideal Gas model

and the ASME Steam Table equation-of-state. (here * refers to pure

component.)

usual for components in activity coefficient models:

The term DHVs(T,p) = Hs*,v - Hs*,ig is the vapor enthalpy departure

contribution to liquid enthalpy; option code 5 determines how this is

calculated.

∞

The property Hk is calculated from the infinite dilution aqueous phase heat

capacity polynomial model, by default. If polynomial model parameters are

not available, it is calculated from the Criss-Cobble model for ions and from

Henry's law for molecular solutes.

The subscript k can refer to a molecular solute defined as a Henry's

component (i), or a cation (c), or an anion (a):

Hm*E is excess enthalpy and is calculated from the electrolyte NRTL activity

coefficient model.

See Criss-Cobble model and Henry's law model for more information.

Option codes can improve the performance of this model when using mixed

solvents and Henry components. See Option Codes for Enthalpy Models for

details.

Parameter Applicable Symbol Default Units

Name Components

IONTYP Ions † Ion 0 —

SO25C Cations ∞,aq — MOLE-ENTROPY

Sc (T=298)

Anions ∞,aq — MOLE-ENTROPY

Sa (T=298)

DHAQFM Ions, Molecular Solutes Δf Hk∞,aq — MOLE-ENTHALPY

††

CPAQ0 Ions, Molecular Solutes ∞,aq — HEAT-CAPACITY

Cp,k

††

DHFORM Molecular Solutes †† Δf Hi*,ig — MOLE-ENTHALPY

*,ig

Water, Solvents Cp,w — †††

†† DHFORM is not used if DHAQFM and CPAQ0 are given for molecular solutes

(components declared as Henry's components). If CPAQ0 is missing, DHFORM

and Henry's constants are used to calculate infinite dilution enthalpy for

solutes.

††† The unit keywords for CPIG are TEMPERATURE and HEAT-CAPACITY. If

CPIG/10 or CPIG/11 is non-zero, then absolute temperature units are

assumed for CPIG/9 through CPIG/11. Otherwise, user input temperature

units are used for all elements of CPIG. User input temperature units are

always used for other elements of CPIG.

The equation for the NRTL Gibbs free energy model is:

The molar Gibbs free energy and the molar excess Gibbs free energy Gm* and

Gm*E are defined with the asymmetrical reference state: as pure water and

infinite dilution of molecular solutes and ions. (* refers to the asymmetrical

reference state.) The ideal mixing term is calculated normally, where j refers

to any component. The molar Gibbs free energy of pure water (or

thermodynamic potential) μw* is calculated from the ideal gas contribution.

This is a function of the ideal gas heat capacity and the departure function.

(here * refers to the pure component.)

μs*,l is the Gibbs free energy contribution from a non-water solvent. It is

calculated as usual for components in activity coefficient models.

∞

The aqueous infinite dilution thermodynamic potential μk is calculated from

the infinite dilution aqueous phase heat capacity polynomial model, by

default. Subscript k refers to any ion or molecular solute. If polynomial model

parameters are not available, it is calculated from the Criss-Cobble model for

ionic solutes:

∞ ∞

Because Δf Hk ,aq and Δf Gk ,aq are based on a molality scale, and μk∞ is based

on mole fraction scale, the term RT ln(1000/Mw) is added.

See the Criss-Cobble model and Henry's law model for more information.

Option codes can improve the performance of this model when using mixed

solvents and Henry components. See Option Codes for Gibbs Energy Models

for details.

Parameter Applicable Symbol Default Units

Name Components

IONTYP Ions † Ion 0 —

SO25C Cations † ∞,aq — MOLE-ENTROPY

Sc (T=298)

Anions † ∞,aq — MOLE-ENTROPY

Sa (T=298)

DGAQFM Ions, Molecular Solutes Δf Gk∞,aq — MOLE-ENTHALPY

††

CPAQ0 Ions, Molecular Solutes ∞,aq — HEAT-CAPACITY

Cp,k

††

DGFORM Molecular Solutes †† Δf Gi — MOLE-ENTHALPY

*,ig

Water, Solvents Cp,w — †††

† IONTYP and SO25C are not needed if CPAQ0 is given for ions.

†† DGFORM is not needed if DHAQFM and CPAQ0 are given for molecular

solutes.

††† The unit keywords for CPIG are TEMPERATURE and HEAT-CAPACITY. If

CPIG/10 or CPIG/11 is non-zero, then absolute temperature units are

assumed for CPIG/9 through CPIG/11. Otherwise, user input temperature

units are used for all elements of CPIG. User input temperature units are

always used for other elements of CPIG.

Correlation

Liquid enthalpy is directly calculated by integration of liquid heat capacity:

Where:

Hi*,ig = Ideal gas enthalpy

Hi*,v - Hi*,ig = Vapor enthalpy departure from equation of state

298.15 K

See DIPPR/IK-CAPE Liquid Heat Capacity for parameter requirement and

additional details.

States

Two property methods, WILS-LR and WILS-GLR, are available to calculate

enthalpies based on different reference states. The WILS-LR property method

is based on saturated liquid reference state for all components. The WILS-GLR

property method allows both ideal gas and saturated liquid reference states

for different components.

These property methods use an enthalpy method that optimizes the accuracy

tradeoff between liquid heat capacity, heat of vaporization, and vapor heat

capacity at actual process conditions. This highly recommended method

eliminates many of the problems associated with accurate thermal properties

for both phases, especially the liquid phase.

The liquid enthalpy of mixture is calculated by the following equation (see the

table labeled Liquid Enthalpy Methods):

Where:

Hmig = Enthalpy of ideal gas mixture

=

(Hml-Hmig) = Enthalpy departure of mixture

For supercritical components, declared as Henry's components, the enthalpy

departure is calculated as follows:

Hml-Hmig =

HmE,l =

H*,ig and H*,l can be calculated based on either saturated liquid or ideal gas as

reference state as described in the sections that follow.

For the WILS-LR property method, H*,ig and H*,l are calculated based on the

saturated liquid reference state for all components.

For the WILS-GLR property method, H*,ig and H*,l can be calculated based on

the saturated liquid reference state for some components and the ideal gas

reference state for other components. You can set the value of a pure

component parameter called RSTATE to specify the reference state for each

component. RSTATE = 1 denotes ideal gas reference state. RSTATE = 2

denotes saturated liquid reference state. If it is not set, the following default

rules apply based on the normal boiling point of the component, i, TB(i):

• If TB(i) <= 298.15 K, ideal gas reference state is used

• If TB(i) > 298.15 K, saturated liquid reference state is used.

The saturated liquid enthalpy at temperature T is calculated as follows:

Where:

Hiref,l = Reference enthalpy for liquid state at Tiref,l

Cp,i*,l = Liquid heat capacity of component i

The saturated liquid Gibbs free energy is calculated as follows:

Where:

Giref,l = Reference Gibbs free energy for liquid state at Tiref,l

p = System pressure

ref

p = Reference pressure (=101325 N/m2)

For the WILS-LR property method, Hiref,l and Giref,l default to zero (0). The

reference temperature Tiref,l defaults to 273.15K.

For the WILS-GLR property method, the reference temperature Tiref,l defaults

to 298.15K and Hiref,l defaults to:

Where:

Hiref,ig = Ideal gas enthalpy of formation for liquid state at

298.15K

Giref,ig = Ideal gas Gibbs free energy of formation for liquid

state at 298.15K

Note that we cannot default the liquid reference enthalpy and Gibbs free

energy to zero, as is the case for WILS-LR, because it will cause inconsistency

with the enthalpy of components that use ideal-gas reference state. The

default values used result in the enthalpies of all components being on the

same basis. In fact, if you enter values for Hiref,l and Giref,l for a liquid-

reference state component you must make sure that they are consistent with

each other and are consistent with the enthalpy basis of the remaining

components in the mixture. If you enter a value for Hiref,l, you should also

enter a value for Giref,l to ensure consistency.

When the liquid-reference state is used, the ideal gas enthalpy at

temperature T is not calculated from the integration of the ideal gas heat

capacity equation (see Ideal Gas as Reference State section below). For

consistency, it is calculated from liquid enthalpy as follows:

Where:

Ticon,l = Temperature of conversion from liquid to vapor

enthalpy for component i

temperature of Tcon,l

conversion temperature and vapor pressure pi*,l

pi*,l = Liquid vapor pressure of component i

= Ideal gas heat capacity of component i

Ticon,l is the temperature at which one crosses from liquid state to the vapor

state. This is a user defined temperature that defaults to the system

temperature T. Ticon,l may be selected such that heat of vaporization for

component i at the temperature is most accurate.

The vapor enthalpy is calculated from ideal gas enthalpy as follows:

Where:

system temperature and pressure

The liquid heat capacity and the ideal gas heat capacity can be calculated

from the ASPEN, DIPPR, IK-CAPE, BARIN, NIST/TDE, or other available

models. The heat of vaporization can be calculated from the Watson, DIPPR,

IK-CAPE, NIST/TDE, or other available models. The enthalpy departure is

obtained from an equation-of-state that is being used in the property method.

For WILS-LR and WILS-GLR, the ideal gas equation of state is used.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

RSTATE † — 2 — — — —

TREFHL Tiref,l †† — — — TEMPERATURE

DHLFRM Hiref,l ††† — — — MOLE ENTHALPY

DGLFRM Giref,l †††† — — — MOLE ENTHALPY

TCONHL Ticon,l T — — — TEMPERATURE

reference state.

†† For WILS-LR property method TREFHL defaults to 273.15K. For WILS-GLR

property method, TREFHL defaults to 298.15 K.

††† For WILS-LR property method, DHLFRM defaults to zero (0). For WILS-

GLR property method, DHLFRM defaults to the equation above.

†††† For WILS-LR property method, DGLFRM defaults to zero (0). For WILS-

GLR property method, DGLFRM defaults to the equation above.

Liquid heat capacity equation is required for all components.

Ideal Gas as Reference State

The saturated liquid enthalpy is calculated as follows:

Where:

Hiref,ig = Reference state enthalpy for ideal gas at Tiref,ig

= Heat of formation of ideal gas at 298.15 K by default

Tiref,ig = Reference temperature corresponding to Hiref,ig.

Defaults to 298.15 K

Ticon,ig = The temperature at which one crosses from vapor

state to liquid state. This is a user defined

temperature that defaults to the system temperature

T. Ticon,igmay be selected such that heat of

vaporization of component i at the temperature is

most accurate.

The ideal gas enthalpy is calculated as follows:

The liquid heat capacity and the ideal gas heat capacity can be calculated

from the ASPEN, DIPPR, IK-CAPE, BARIN, NIST/TDE, or other available

models. The heat of vaporization can be calculated from the Watson, DIPPR,

IK-CAPE, NIST/TDE, or other available models. The enthalpy departure is

obtained from an equation of state that is being used in the property method.

For WILS-LR and WILS-GLR, the ideal gas equation of state is used.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

RSTATE — 1† — — — —

TREFHI Tiref,ig †† — — — TEMPERATURE

DHFORM Hiref,ig — — — — MOLE ENTHALPY

TCONHI Ticon,ig T — — — TEMPERATURE

gas.

TREFHI defaults to 298.15 K. For components with TB > 298.15 K, RSTATE

defaults to 2 (liquid) and TREFHI does not apply to these components. See

the Saturated Liquid as Reference State section for more details.

Helgeson Equations of State

The Helgeson equations of state for standard volume , heat capacity ,

entropy , enthalpy of formation , and Gibbs energy of formation

at infinite dilution in aqueous phase are:

Where:

Where:

water)

ω = Born coefficient

Pr = Reference pressure (1 bar)

temperature units.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

AHGPAR/1, ... , a1, ..., a4 0 — — — —

4

CHGPAR/1, ... , c1, c2 x — — — —

2

DHAQHG 0 — -0.5x1010 0.5x1010 MOLE-ENTHALPY

References

Tanger, J.C. IV and H.C. Helgeson, "Calculation of the thermodynamic and

transport properties of aqueous species at high pressures and temperatures:

Revised equation of state for the standard partial properties of ions and

electrolytes," American Journal of Science, Vol. 288, (1988), p. 19-98.

Shock, E.L. and H.C. Helgeson, "Calculation of the thermodynamic and

transport properties of aqueous species at high pressures and temperatures:

Correlation algorithms for ionic species and equation of state predictions to 5

kb and 1000 °C," Geochimica et Cosmochimica Acta, Vol. 52, p. 2009-2036.

Shock, E.L., H.C. Helgeson, and D.A. Sverjensky, "Calculation of the

thermodynamic and transport properties of aqueous species at high pressures

and temperatures: Standard partial molal properties of inorganic neutral

species," Geochimica et Cosmochimica Acta, Vol. 53, p. 2157-2183.

The quadratic mixing rule is a general-purpose mixing rule which can be

applied to various properties. For a given property Q, with i and j being

components, the rule is:

The pure component properties Qi and Qj are calculated by the default model

for that property, unless modified by option codes. Composition xi and xj is in

mole fraction unless modified by option codes. Kij is a binary parameter

specific to the mixing rule for each property. A variation on the equation using

the logarithm of the property is used for viscosity.

3 Transport Property Models

This section describes the transport property models available in the Aspen

Physical Property System. The following table provides an overview of the

available models. This table lists the Aspen Physical Property System model

names, and their possible use in different phase types, for pure components

and mixtures.

Viscosity models Model name Phase(s) Pure Mixture

Andrade Liquid Mixture MUL2ANDR L — X

Viscosity

Andrade/DIPPR/PPDS/IK-CAPE MUL0ANDR L X —

API Liquid Viscosity MUL2API L — X

API 1997 Liquid Viscosity MULAPI97 L — X

Aspen Liquid Mixture Viscosity MUASPEN L — X

ASTM Liquid Mixture Viscosity MUL2ASTM L — X

Chapman-Enskog-Brokaw MUV0CEB V X —

/DIPPR/PPDS/IK-CAPE

Chapman-Enskog-Brokaw- MUV2BROK, V — X

Wilke Mixing Rule MUV2WILK

Chung-Lee-Starling Low MUV0CLSL, V X X

Pressure MUV2CLSL

Chung-Lee-Starling MUV0CLS2, VL X X

MUV2CLS2,

MUL0CLS2,

MUL2CLS2

Dean-Stiel Pressure Correction MUV0DSPC, V X X

MUV2DSPC

IAPS Viscosity MUV0H2O V X —

MUL0H2O L X —

Jones-Dole Electrolyte MUL2JONS L — X

Correction

Letsou-Stiel MUL0LEST, L X X

MUL2LEST

Lucas MUV0LUC, V X X

MUV2LUC

Viscosity models Model name Phase(s) Pure Mixture

TRAPP viscosity MUL0TRAP, VL X X

MUL2TRAP,

MUV0TRAP,

MUV2TRAP

Twu liquid viscosity MUL2TWU L — X

Viscosity quadratic mixing rule MUL2QUAD L — X

models

Chung-Lee-Starling Thermal KV0CLS2, VL X X

Conductivtity KV2CLS2,

KL0CLS2,

KL2CLS2

IAPS Thermal Conductivity for KV0H2O V X —

Water KL0H2O L X —

Li Mixing Rule KL2LI L X X

Riedel Electrolyte Correction KL2RDL L — X

Sato-Riedel/DIPPR/PPDS/ IK- KL0SR, L X X

CAPE KL2SRVR

Stiel-Thodos/DIPPR/PPDS/ IK- KV0STLP V X —

CAPE

Stiel-Thodos Pressure KV0STPC, V X X

Correction KV2STPC

TRAPP Thermal Conductivity KV0TRAP, VL X X

KV2TRAP,

KL0TRAP,

KL2TRAP

Vredeveld Mixing Rule KL2SRVR L X X

Wassiljewa-Mason-Saxena KV2WMSM V X X

mixing rule

Chapman-Enskog-Wilke-Lee DV0CEWL V — X

Binary

Chapman-Enskog-Wilke-Lee DV1CEWL V — X

Mixture

Dawson-Khoury-Kobayashi DV1DKK V — X

Binary

Dawson-Khoury-Kobayashi DV1DKK V — X

Mixture

Nernst-Hartley Electrolytes DL0NST, L — X

DL1NST

Wilke-Chang Binary DL0WC2 L — X

Wilke-Chang Mixture DL1WC L — X

Liquid Mixture Surface Tension SIG2IDL L — X

API Surface Tension SIG2API L — X

Surface tension models Model name Phase(s) Pure Mixture

Hakim-Steinberg-Stiel/DIPPR SIG0HSS, L X —

/IK-CAPE SIG2HSS

IAPS surface tension SIG0H2O L X —

Onsager-Samaras Electrolyte SIG2ONSG L — X

Correction

Modified MacLeod-Sugden SIG2MS L — X

Viscosity Models

The Aspen Physical Property System has the following built-in viscosity

models:

Model Type

Andrade Liquid Mixture Viscosity Liquid

Andrade/DIPPR/PPDS/IK-CAPE Pure component liquid

API liquid viscosity Liquid

API 1997 liquid viscosity Liquid

Chapman-Enskog-Brokaw/DIPPR/IK-CAPE Low pressure vapor,

pure components

Chapman-Enskog-Brokaw-Wilke Mixing Rule Low pressure vapor,

mixture

Chung-Lee-Starling Low Pressure Low pressure vapor

Chung-Lee-Starling Liquid or vapor

Dean-Stiel Pressure correction Vapor

IAPS viscosity Water or steam

Jones-Dole Electrolyte Correction Electrolyte

Letsou-Stiel High temperature liquid

Lucas Vapor

TRAPP viscosity Vapor or liquid

Aspen Liquid Mixture Viscosity Liquid

ASTM Liquid Mixture Viscosity Liquid

Twu liquid viscosity Liquid

Viscosity quadratic mixing rule Liquid

The liquid mixture viscosity is calculated by the modified Andrade equation:

Where:

kij =

mij =

If first option code of Then fi is

MUL2ANDR is

0 (Default) Mole fraction of component i

1 Mass fraction of component i

Note that the Andrade liquid mixture viscosity model is called from other

models. The first option codes of these models cause fi to be mole or mass

fraction when Andrade is used in the respective models. To maintain

consistency across models, if you set the first option code for MUL2ANDR to

1, you should also the set the first option code of the other models to 1, if

they are used in your simulation.

Model Model Name

MUL2JONS Jones-Dole Electrolyte Viscosity model

DL0WCA Wilke-Chang Diffusivity model (binary)

DL1WCA Wilke-Chang Diffusivity model (mixture)

DL0NST Nernst-Hartley Electrolyte Diffusivity model (binary)

DL1NST Nernst-Hartley Electrolyte Diffusivity model (mixture)

The binary parameters kij and mij allow accurate representation of complex

liquid mixture viscosity. Both binary parameters default to zero.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

ANDKIJ/1 aij 0 — — — —

ANDKIJ/2 bij 0 — — — —

ANDMIJ/1 cij 0 — — — —

ANDMIJ/2 dij 0 — — — —

equations:

• Andrade

• DIPPR

• IK-CAPE

See the Andrade/DIPPR/IK-CAPE Pure Component Liquid Viscosity model for

descriptions.

Andrade/DIPPR/PPDS/IK-CAPE Pure

Component Liquid Viscosity

The Aspen Physical Property System has several submodels for calculating

pure component liquid viscosity. It uses parameter TRNSWT/1 to determine

which submodel is used. See Pure Component Temperature-Dependent

Properties for details.

If TRNSWT/1 is This equation is used And this parameter is used

0 Andrade MULAND

If TRNSWT/1 is This equation is used And this parameter is used

101 DIPPR MULDIP

301 PPDS MULPDS

401 IK-CAPE polynomial equation MULPO

404 IK-CAPE exponential equation MULIKC

508 NIST TDE equation MULNVE

509 NIST PPDS9 MULPPDS9

The Andrade equation is:

outside bounds.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

MULAND/1 Ai — X — — VISCOSITY,

TEMPERATURE †

MULAND/2 Bi — X — — TEMPERATURE †

MULAND/3 Ci — X — — TEMPERATURE †

MULAND/4 Tl 0.0 X — — TEMPERATURE

MULAND/5 Th 500.0 X — — TEMPERATURE

and Ci. Otherwise, all coefficients are interpreted in user input temperature

units. The temperature limits are always interpreted in user input units.

The equation for the DIPPR liquid viscosity model is:

outside bounds.

(Other DIPPR equations may sometimes be used. See Pure Component

Temperature-Dependent Properties for details.)

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

MULDIP/1 C1i — X — — VISCOSITY,

TEMPERATURE ††

MULDIP/2, ..., 5 C2i, ..., C5i 0 X — — TEMPERATURE ††

MULDIP/6 C6i 0 X — — TEMPERATURE

MULDIP/7 C7i 1000 X — — TEMPERATURE

†† If any of C3i through C5i are non-zero, absolute temperature units are

assumed for C3i through C5i. Otherwise, all coefficients are interpreted in user

input temperature units. The temperature limits are always interpreted in

user input units.

PPDS

The PPDS equation is:

bounds.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

MULPDS/1 C1i — — — — —

MULPDS/2 C2i — — — —

MULPDS/3 C3i — — — TEMPERATURE

MULPDS/4 C4i — — — TEMPERATURE

MULPDS/5 C5i — — — — VISCOSITY

MULPDS/6 C6i — — — TEMPERATURE

MULPDS/7 C7i — — — TEMPERATURE

This is the same as the PPDS equation above, but it uses parameter

MULPPDS9. Note that the parameters are in a different order.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

MULPPDS9/1 C5i — — — — Pa*S

MULPPDS9/2 C1i — — — —

MULPPDS9/3 C2i — — — TEMPERATURE

MULPPDS9/4 C3i — — — TEMPERATURE

MULPPDS9/5 C4i — — — — TEMPERATURE

MULPPDS9/6 C6i — — — TEMPERATURE

MULPPDS9/7 C7i — — — TEMPERATURE

The IK-CAPE liquid viscosity model includes both exponential and polynomial

equations.

Exponential

bounds.

Parameter SymbolDefault MDS Lower Upper Units

Name/Element Limit Limit

MULIKC/1 C1i — X — — VISCOSITY

Parameter SymbolDefault MDS Lower Upper Units

Name/Element Limit Limit

MULIKC/2 C2i 0 X — — TEMPERATURE †††

MULIKC/3 C3i 0 X — — VISCOSITY

MULIKC/4 C4i 0 X — — TEMPERATURE

MULIKC/5 C5i 1000 X — — TEMPERATURE

††† Absolute temperature units are assumed for C2i. The temperature limits

are always interpreted in user input units.

Polynomial

bounds.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

MULPO/1 C1i — X — — VISCOSITY

MULPO/2, ..., 10 C2i, ..., C10i 0 X — — VISCOSITY,

TEMPERATURE

MULPO/11 C11i 0 X — — TEMPERATURE

MULPO/12 C12i 1000 X — — TEMPERATURE

bounds.

Absolute temperature units are assumed for C2i, C3i, and C4i. The temperature

limits are always interpreted in user input units.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

MULNVE/1 C1i — X — — —

MULNVE/2, 3, 4 C2i, C3i, C4i 0 X — — TEMPERATURE

MULNVE/5 C5i 0 X — — TEMPERATURE

MULNVE/6 C6i 1000 X — — TEMPERATURE

References

R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and

Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 439.

API Liquid Viscosity

The liquid mixture viscosity is calculated using a combination of the API and

Andrade/DIPPR equations. This model is recommended for petroleum and

petrochemical applications. It is used in the CHAO-SEA, GRAYSON, LK-PLOCK,

PENG-ROB, and RK-SOAVE option sets.

For pseudocomponents, the API model is used:

Where:

fcn = A correlation based on API Procedures and Figures 11A4.1, 11A4.2,

and 11A4.3 (API Technical Data Book, Petroleum Refining, 4th

edition)

Vml is obtained from the API liquid volume model.

For real components, the Andrade/DIPPR model is used.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

TB Tbi — — 4.0 2000.0 TEMPERATURE

API APIi — — -60.0 500.0 —

The liquid mixture viscosity is calculated using a combination of the API and

Andrade/DIPPR equations. This model is recommended over the earlier API

viscosity model.

This model is applicable to petroleum fractions with normal boiling points from

150 F to 1200 F and API gravities between 0 and 75. Testing by AspenTech

indicates that this model is slightly more accurate than the Twu model for

light and medium boiling petroleum components, while the Twu model is

superior for heavy fractions.

For pseudocomponents, the API model is used:

Where:

fcn = A correlation based on API Procedures and Figures 11A4.2, 11A4.3,

and 11A4.4 (API Technical Data Book, Petroleum Refining, 1997

edition)

Vml is obtained from the API liquid volume model.

For real components, the Andrade/DIPPR model is used.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

TB Tbi — — 4.0 2000.0 TEMPERATURE

API APIi — — -60.0 500.0 —

Aspen Liquid Mixture Viscosity

The liquid mixture viscosity is calculated by the equation:

Where:

Xi = Mole fraction or weight fraction of component i

kij = Symmetric binary parameter (kij = kji)

lij = Antisymmetric binary parameter (lij = -lji)

equations:

• Andrade

• DIPPR

• IK-CAPE

See the Andrade/DIPPR/IK-CAPE Pure Component Liquid Viscosity model for

descriptions.

The binary parameters kij and lij allow accurate representation of complex

liquid mixture viscosity. Both binary parameters default to zero.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

MUKIJ kij 0 — -100.0 100.0 —

MULIJ lij 0 — 100.0 100.0 —

It is generally difficult to predict the viscosity of a mixture of viscous

components. For hydrocarbons, the following weighting method (ASTM †) is

known to give satisfactory results:

Where:

wi = Weight fraction of component i

f = An adjustable parameter, typically in the

range of 0.5 to 1.0

The individual component viscosities are calculated by the Andrade, DIPPR, or

IK-CAPE equation. The parameter f can be specified by setting the value for

MULOGF for the first component in the component list (as defined on the

Components | Specifications | Selection sheet).

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

MULOGF f 1.0 — 0.0 2.0 —

Institut Francais du Petrole Publications, 1995, p. 130.

Chapman-Enskog-

Brokaw/DIPPR/PPDS/IK-CAPE Vapor

Viscosity

The Aspen Physical Property System has several submodels for calculating

pure component low pressure vapor viscosity. It uses parameter TRNSWT/2

to determine which submodel is used. See Pure Component Temperature-

Dependent Properties for details.

If TRNSWT/2 is This equation is used And this parameter is

used

0 Chapman-Enskog- —

Brokaw

102 DIPPR MUVDIP

301 PPDS MUVPDS

302 PPDS kinetic theory MUVCEB

401 IK-CAPE polynomial MUVPO

equation

402 IK-CAPE Sutherland MUVSUT

equation

503 NIST ThermoML MUVTMLPO

polynomial

Chapman-Enskog-Brokaw

The equation for the Chapman-Enskog model is:

Where:

Ωη =

Lennard-Jones potential parameters for ε/k (energy parameter) and σ

(collision diameter). To calculate δ, the dipole moment p and either the

Stockmayer parameters or Tb and Vb are needed. The polarity correction is

from Brokaw.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

MW Mi — — 1.0 5000.0 —

-24

MUP pi — — 0.0 5x10 DIPOLEMOMENT

STKPAR/1 (εi/k) ST fcn(Tbi, Vbi, pi) — X — TEMPERATURE

The equation for the DIPPR vapor viscosity model is:

range linearly with respect to T, using the slope at the temperature limits.

(Other DIPPR equations may sometimes be used. See Pure Component

Temperature-Dependent Properties for details.)

PCES uses the DIPPR equation in estimating vapor viscosity.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

MUVDIP/1 C1i — X — — VISCOSITY

MUVDIP/2 C2i 0 X — — —

MUVDIP/3, 4 C3i, C4i 0 X — — TEMPERATURE †

MUVDIP/5 †† 0 X — — —

MUVDIP/6 C6i 0 X — — TEMPERATURE

MUVDIP/7 C7i 1000 X — — TEMPERATURE

† If any of C2i through C4i are non-zero, absolute temperature units are

assumed for C1i through C4i. Otherwise, all coefficients are interpreted in user

input temperature units. The temperature limits are always interpreted in

user input units.

†† MUVDIP/5 is not used in this equation. It is normally set to zero. The

parameter is provided for consistency with other DIPPR equations.

PPDS

The PPDS submodel includes both the basic PPDS vapor viscosity equation

and the PPDS kinetic theory vapor viscosity equation. For either equation,

linear extrapolation of viscosity versus T occurs for temperatures outside

bounds.

The equation is:

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

MUVPDS/1 C1i — — — — VISCOSITY

MUVPDS/2 C2i 0 — — — —

MUVPDS/3 C3i 0 — — — —

MUVPDS/4 C4i 0 — — — TEMPERATURE

MUVPDS/5 C5i 1000 — — — TEMPERATURE

The equation is:

Name/Element Limit Limit

MW Mi — — 1.0 5000.0 —

MUVCEB/1 C1i — — — — LENGTH

MUVCEB/2 C2i — — — — TEMPERATURE †

MUVCEB/3 C3i 0 — — — —

MUVCEB/4 C4i 0 — — — TEMPERATURE

MUVCEB/5 C5i 1000 — — — TEMPERATURE

† Absolute temperature units are assumed for C2i . The temperature limits are

always interpreted in user input units.

The IK-CAPE vapor viscosity model includes both the Sutherland equation and

the polynomial equation. For either equation, linear extrapolation of viscosity

versus T occurs for temperatures outside bounds.

Sutherland Equation

Name/Element Limit Limit

MUVSUT/1 C1i — X — — VISCOSITY

MUVSUT/2 C2i 0 X — — TEMPERATURE ††

MUVSUT/3 C3i 0 X — — TEMPERATURE

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

MUVSUT/4 C4i 1000 X — — TEMPERATURE

†† If C2i is non-zero, absolute temperature units are assumed for C1i and C2i.

Otherwise, all coefficients are interpreted in user input temperature units. The

temperature limits are always interpreted in user input units.

Polynomial

Name/Element Limit Limit

MUVPO/1 C1i — X — — VISCOSITY

MUVPO/2, ..., 10 C2i, ..., C10i 0 X — — VISCOSITY,

TEMPERATURE

MUVPO/11 C11i 0 X — — TEMPERATURE

MUVPO/12 C12i 1000 X — — TEMPERATURE

Name/Element Limit Limit

MUVTMLPO/1 C1i — X — — Pa*s/T

MUVTMLPO/2, ..., 4 C2i , ..., C4i 0 X — — Pa*s/T

MUVTMLPO/5 nTerms 4 X — — —

MUVTMLPO/6 Tlower 0 X — — TEMPERATURE

MUVTMLPO/7 Tupper 1000 X — — TEMPERATURE

References

R.C. Reid, J.M. Prausnitz, and B.E. Poling. The Properties of Gases and

Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 392.

Chapman-Enskog-Brokaw-Wilke Mixing

Rule

The low pressure vapor mixture viscosity is calculated by the Wilke

approximation of the Chapman-Enskog equation:

For Φij,the formulation by Brokaw is used:

Where:

parameter) and σ (collision diameter) and the dipole moment p are used to

calculate δ. The k represents Boltzmann's constant 1.38065 x 10-23 J/K. If the

Stockmayer parameters are not available, δ is estimated from Tb and Vb:

Where p is in debye.

The pure component vapor viscosity ηi*,v (p = 0) can be calculated using the

Chapman- Enskog-Brokaw/DIPPR (or another) low pressure vapor viscosity

model.

Parameter Symbol Default MDS Lower Upper Units

Name/ Limit Limit

Element

MW Mi — — 1.0 5000.0 —

-24

MUP pi — — 0.0 5x10 DIPOLEMOMENT

Parameter Symbol Default MDS Lower Upper Units

Name/ Limit Limit

Element

STKPAR/1 (εi/k)ST fcn(Tbi, Vbi, pi) — X — TEMPERATURE

References

R.C. Reid, J.M. Prausnitz, and T.K. Sherwood, The Properties of Gases and

Liquids, 3rd ed., (New York: McGraw-Hill, 1977), pp. 410–416.

Viscosity

The low-pressure vapor viscosity by Chung, Lee, and Starling is:

C1 is a constant of correlation.

The polar parameter κ is tabulated for certain alcohols and carboxylic acids.

The previous equations can be used for mixtures when applying these mixing

rules:

Where:

Vcij =

Tcij =

ωij =

Mij =

κij =

temperature units.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

TCCLS Tci TC x 5.0 2000.0 TEMPERATURE

VCCLS Vci VC x 0.001 3.5 MOLE-VOLUME

MW Mi — — 1.0 5000.0 —

-24

MUP pi — — 0.0 5x10 DIPOLEMOMENT

OMGCLS ωi OMEGA x -0.5 2.0 —

and the Chung-Lee-Starling Thermal Conductivity models.

References

R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and

Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 396, p. 413.

Chung-Lee-Starling Viscosity

The Chung-Lee-Starling viscosity equation for vapor and liquid, high and low

pressure is:

With:

f1 =

f2 =

FC =

example, the Benedict-Webb-Rubin). The parameter pr is the reduced

dipolemoment:

The polar parameter κ is tabulated for certain alcohols and carboxylic acids.

For low pressures, f1 is reduced to 1.0 and f2 becomes negligible. The

equation reduces to the low pressure vapor viscosity model by Chung-Lee and

Starling.

The previous equations can be used for mixtures when applying these mixing

rules:

Where:

Vcij =

Tcij =

ωij =

Mij =

κij =

Name/Element Limit Limit

TCCLS Tci TC x 5.0 2000.0 TEMPERATURE

VCCLS Vci VC x 0.001 3.5 MOLE-VOLUME

MW Mi — — 1.0 5000.0 —

-24

MUP pi — — 0.0 5x10 DIPOLEMOMENT

OMGCLS ωi OMEGA x -0.5 2.0 —

Thermal Conductivity and Low Pressure Viscosity models as well.

References

R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and

Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 427.

Dean-Stiel Pressure Correction

The residual vapor viscosity or the pressure correction to low pressure vapor

viscosity by Dean and Stiel is:

example, Chapman-Enskog-Brokaw). The dimensionless-making factor ξ is:

ξ =

Tc =

M =

pc =

Vcm =

Zcm =

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

MW Mi — — 1.0 5000.0 —

VC Vci — — 0.001 3.5 MOLE-VOLUME

The IAPS viscosity models, developed by the International Association for

Properties of Steam, calculate vapor and liquid viscosity for water and steam.

These models are used in option sets STEAMNBS and STEAM-TA.

The general form of the equation for the IAPS viscosity models is:

ηw=fcn(T, p)

Where:

fcn = Correlation developed by IAPS

The models are only applicable to water. There are no parameters required

for the models.

Jones-Dole Electrolyte Correction

The Jones-Dole model calculates the correction to the liquid mixture viscosity

of a solvent mixture, due to the presence of electrolytes:

Where:

calculated by the Andrade/DIPPR model

apparent electrolyte ca

option code 3 for MUL2JONS:

Option Code Solvent liquid mixture viscosity

Value model

Andrade liquid mixture viscosity

0

model (default)

1 Viscosity quadratic mixing rule

2 Aspen liquid mixture viscosity

model

If these parameters are available Use this equation

†

IONMOB and IONMUB Jones-Dole

IONMUB Breslau-Miller

— Carbonell

Miller equation is used instead.

Jones-Dole

The Jones-Dole equation is:

(1)

Where:

= Concentration of apparent electrolyte ca (2)

Aca = (4)

La = (5)

Lc = (6)

Bca = (7)

is used instead. This behavior can be disabled by setting the second option

code for MUL2JONS to 0.

Breslau-Miller

The Breslau-Miller equation is:

(8)

(9)

(9a)

Carbonell

The Carbonell equation is:

(10)

Where:

Mk = Molecular weight of an apparent electrolyte

component k

You must provide parameters for the model used for the calculation of the

liquid mixture viscosity of the solvent mixture.

Parameter Symbol Default Lower Upper Units

Name/Element Limit Limit

CHARGE z 0.0 — — —

MW M — 1.0 5000.0 —

IONMOB/1 l1 — — — AREA, MOLES

IONMOB/2 l2 0.0 — — AREA, MOLES,

TEMPERATURE

IONMUB/1 b1 — — — MOLE-VOLUME

IONMUB/2 b2 0,0 — — MOLE-VOLUME,

TEMPERATURE

References

A. L. Horvath, Handbook of Aqueous Electrolyte Solutions, (Chichester: Ellis

Horwood, 1985).

Letsou-Stiel

The Letsou-Stiel model calculates liquid viscosity at high temperatures for

0.76 ≤ Tr ≤ 0.98. This model is used in PCES.

temperature units.

The general form for the model is:

Where:

(ηlε)0 =

(ηlε)1 =

ε =

ω =

Name/Element Limit Limit

MW Mi — — 1.0 5000.0 —

TC Tci — — 5.0 2000.0 TEMPERATURE

PC pci — — 105 108 PRESSURE

OMEGA ωi — — -0.5 2.0 —

References

R.C. Reid, J.M. Pransnitz, and B.E. Poling, The Properties of Gases and

Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 471.

The equation for the Lucas vapor viscosity model is:

The pressure correction factor Y is:

The polar and quantum correction factors at high and low pressure are:

FP =

FQ =

FPi (p = 0) =

gates i = H2, D2, and He.

temperature units.

The Lucas mixing rules are:

Tc =

pc =

M =

FP (p = 0) =

FQ (p = 0) =

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

TCLUC Tci TC x 5.0 2000.0 TEMPERATURE

5 8

PCLUC pci PC x 10 10 PRESSURE

ZCLUC Zci ZC x 0.1 0.5 —

MW Mi — — 1.0 5000.0 —

-24

MUP pi — — 0.0 5x10 DIPOLEMOMENT

References

R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and

Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 421, 431.

TRAPP Viscosity Model

The general form for the TRAPP viscosity model is:

Where:

The parameter is the mole fraction vector; fcn is a corresponding states

correlation based on the model for vapor and liquid viscosity TRAPP, by the

National Bureau of Standards (NBS, currently NIST) . The model can be used

for both pure components and mixtures. The model should be used for

nonpolar components only.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

MW Mi — — 1.0 5000.0 —

TCTRAP Tci TC x 5.0 2000.0 TEMPERATURE

5 8

PCTRAP pci PC x 10 10 PRESSURE

VCTRAP Vci VC x 0.001 3.5 MOLE-VOLUME

ZCTRAP Zci ZC x 0.1 1.0 —

OMGRAP ωi OMEGA x -0.5 3.0 —

References

J.F. Ely and H.J.M. Hanley, "Prediction of Transport Properties. 1. Viscosities

of Fluids and Mixtures," Ind. Eng. Chem. Fundam., Vol. 20, (1981), pp. 323–

332.

The Twu liquid viscosity model is based upon the work of C.H. Twu (1985).

The correlation uses n-alkanes as a reference fluid and is capable of

predicting liquid viscosity for petroleum fractions with normal boiling points up

to 1340 F and API gravity up to -30.

Given the normal boiling point Tb and the specific gravity SG of the system to

be modeled, the Twu model estimates the viscosity of the n-alkane reference

fluid of the same normal boiling point at 100 F and 210 F, and its specific

gravity. These are used to estimates the viscosity of the system to be

modeled at 100 F and at 210 F, and these viscosities are used to estimate the

viscosity at the temperature of interest.

Where:

SG = Specific gravity of petroleum fraction

Tb = Normal boiling point of petroleum fraction, Rankine

SG° = Specific gravity of reference fluid with normal

boiling point Tb

T = Temperature of petroleum fraction, Rankine

(i=1) and 210 F (i=2), cSt

210 F, cSt

Tc° = Critical temperature of reference fluid, Rankine

Reference

C.H. Twu, "Internally Consistent Correlation for Predicting Liquid Viscosities of

Petroleum Fractions," Ind. Eng. Chem. Process Des. Dev., Vol. 24 (1985), pp.

1287-1293

With i and j being components, the viscosity quadratic mixing rule is:

CAPE model.

Option Codes

Option Code Value Descriptions

1 0 Use mole basis composition (default)

1 Use mass basis composition

Parameter

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

MLQKIJ Kij - x - - —

The Aspen Physical Property System has eight built-in thermal conductivity

models. This section describes the thermal conductivity models available.

Model Type

Chung-Lee-Starling Vapor or liquid

IAPS Water or steam

Li Mixing Rule Liquid mixture

Riedel Electrolyte Correction Electrolyte

Sato-Riedel/DIPPR/IK-CAPE Liquid

Solid Thermal Conductivity Polynomial Solid

Stiel-Thodos/DIPPR/IK-CAPE Low pressure vapor

Stiel-Thodos Pressure Correction Vapor

TRAPP Thermal Conductivity Vapor or liquid

Vredeveld Mixing Rule Liquid mixture

Wassiljewa-Mason-Saxena Mixing Rule Low pressure vapor

Chung-Lee-Starling Thermal Conductivity

The main equation for the Chung-Lee-Starling thermal conductivity model is:

Where:

f1 =

f2 =

Ψ =

molar density can be calculated using an equation-of-state model (for

example, the Benedict-Webb-Rubin equation-of-state). The parameter pr is

the reduced dipolemoment:

The polar parameter κ is tabulated for certain alcohols and carboxylic acids.

For low pressures, f1 is reduced to 1.0 and f2 is reduced to zero. This gives

the Chung-Lee-Starling expression for thermal conductivity of low pressure

gases.

The same expressions are used for mixtures. The mixture expression for η (p

= 0) must be used. (See Chung-Lee-Starling Low-Pressure Vapor Viscosity.)

Where:

Vcij =

Tcij =

ωij =

Mij =

κij =

Name/Element Limit Limit

TCCLS Tci TC x 5.0 2000.0 TEMPERATURE

VCCLS Vci VC x 0.001 3.5 MOLE-VOLUME

MW Mi — — 1.0 5000.0 —

-24

MUP pi — — 0.0 5x10 DIPOLEMOMENT

OMGCLS ωi OMEGA x -0.5 2.0 —

Starling Viscosity models.

References

R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and

Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 505, 523.

The IAPS thermal conductivity models were developed by the International

Association for Properties of Steam. These models can calculate vapor and

liquid thermal conductivity for water and steam. They are used in option sets

STEAMNBS and STEAM-TA.

The general form of the equation for the IAPS thermal conductivity models is:

λw=fcn(T, p)

Where:

fcn = Correlation developed by IAPS

The models are only applicable to water. No parameters are required.

Li Mixing Rule

Liquid mixture thermal conductivity is calculated using Li equation (Reid

et.al., 1987):

Where:

The pure component liquid molar volume Vi*,l is calculated from the Rackett

model.

three models:

• Sato Riedel

• DIPPR

• IK-CAPE

See the Sato Riedel/DIPPR/IK-CAPE model for descriptions.

Reference: R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases

and Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 550.

The Riedel model can calculate the correction to the liquid mixture thermal

conductivity of a solvent mixture, due to the presence of electrolytes:

Where:

calculated by the Sato-Riedel model using the

Vredeveld mixing rule

xcaa = Mole fraction of the apparent electrolyte ca

ac, aa = Riedel ionic coefficient

Vml = Apparent molar volume computed by the Clarke

density model

Apparent electrolyte mole fractions are computed from the true ion mole-

fractions and ionic charge number. They can also be computed if you use the

apparent component approach. A more detailed discussion of this method is

found in Electrolyte Calculation.

You must provide parameters for the Sato-Riedel model. This model is used

for the calculation of the thermal conductivity of solvent mixtures.

Parameter Symbol Default Lower Upper Units

Name/Element Limit Limit

CHARGE z 0.0 — — —

IONRDL a 0.0 — — †

The behavior of this model can be changed using option codes (these codes

apply to the Vredeveld mixing rule).

Option Option Description

Code Value

1 0 Do not check ratio of KL max / KL min

1 Check ratio. If KL max / KL min > 2, set exponent to 1,

overriding option code 2.

2 0 Exponent is -2

1 Exponent is 0.4

2 Exponent is 1. This uses a weighted average of liquid thermal

conductivities.

Sato-Riedel/DIPPR/IK-CAPE Liquid

Thermal Conductivity

The Aspen Physical Property System has several submodels for calculating

pure component liquid thermal conductivity. It uses parameter TRNSWT/3 to

determine which submodel is used. See Pure Component Temperature-

Dependent Properties for details.

If TRNSWT/3 is This equation is used And this parameter is used

0 Sato-Riedel —

100 DIPPR KLDIP

301 PPDS KLPDS

401 IK-CAPE KLPO

503 NIST ThermoML KLTMLPO

polynomial

510 NIST PPDS8 equation KLPPDS8

Sato-Riedel

The Sato-Riedel equation is (Reid et al., 1987):

Where:

Tbri = Tbi / Tci

Tri = T / Tci

temperature units.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

MW Mi — — 1.0 5000.0 —

TC Tci — — 5.0 2000.0 TEMPERATURE

TB Tbi — — 4.0 2000.0 TEMPERATURE

PPDS

The equation is:

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

KLPDS/1 C1i — — — — THERMAL-

CONDUCTIVITY

KLPDS/2 C2i 0 — — — —

KLPDS/3 C3i 0 — — — —

KLPDS/4 C4i 0 — — — —

KLPDS/5 C5i 0 — — — TEMPERATURE

KLPDS/6 C6i 1000 — — — TEMPERATURE

The equation is

Name/Element Limit Limit

KLPPDS8/1 C1i — — — — THERMAL-

CONDUCTIVITY

KLPPDS8/2, ..., 7 C2i , ..., C7i 0 — — — —

KLPPDS8/8 TCi — — — — TEMPERATURE

KLPPDS8/9 nTerms 7 — — — —

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

KLPPDS8/10 Tlower 0 — — — TEMPERATURE

KLPPDS8/11 Tupper 1000 — — — TEMPERATURE

The DIPPR equation is:

(Other DIPPR equations may sometimes be used. See Pure Component

Temperature-Dependent Properties for details.)

The DIPPR equation is used by PCES when estimating liquid thermal

conductivity.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

KLDIP/1 C1i — x — — THERMAL-

CONDUCTIVITY,

TEMPERATURE

KLDIP/2, ... , 5 C2i , ..., C5i 0 x — — THERMAL-

CONDUCTIVITY,

TEMPERATURE

KLDIP/6 C6i 0 x — — TEMPERATURE

KLDIP/7 C7i 1000 x — — TEMPERATURE

The equation is:

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

KLTMLPO/1 C1i — x — — THERMAL-

CONDUCTIVITY,

TEMPERATURE

KLTMLPO/2, ... , C2i , ..., C4i 0 x — — THERMAL-

4 CONDUCTIVITY,

TEMPERATURE

KLTMLPO/5 nTerms 4 x — — —

KLTMLPO/6 Tlower 0 x — — TEMPERATURE

KLTMLPO/7 Tupper 1000 x — — TEMPERATURE

IK-CAPE

The IK-CAPE equation is:

Linear extrapolation of λ*,l versus T occurs outside of bounds.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

KLPO/1 C1i — x — — THERMAL-

CONDUCTIVITY

KLPO/2, ... , 10 C2i , ..., C10i 0 x — — THERMAL-

CONDUCTIVITY,

TEMPERATURE

KLPO/11 C11i 0 x — — TEMPERATURE

KLPO/12 C12i 1000 x — — TEMPERATURE

References

R.C. Reid, J.M. Prausnitz, and T.K. Sherwood, The Properties of Gases and

Liquids, 4th ed., (New York: McGraw-Hill, 1977), p. 533.

R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and

Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 550.

Thermal conductivity for solid pure components is calculated using the solid

thermal conductivity polynomial. For mixtures, the mole-fraction weighted

average is used.

For pure solids, thermal conductivity is calculated by:

For mixtures:

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

KSPOLY/1 a — — — — THERMAL

CONDUCTIVITY

KSPOLY/2, 3, 4, 5 b, c, d, e — — — — THERMAL

CONDUCTIVITY,

TEMPERATURE

KSPOLY/6 0 x — — TEMPERATURE

Stiel-Thodos/DIPPR/PPDS/IK-CAPE Vapor

Thermal Conductivity

The Aspen Physical Property System has several submodels for calculating

pure component low pressure vapor thermal conductivity. It uses parameter

TRNSWT/4 to determine which submodel is used. See Pure Component

Temperature-Dependent Properties for details.

If TRNSWT/4 is This equation is used And this parameter is

used

0 Stiel-Thodos —

102 DIPPR KVDIP

301 PPDS KVPDS

401 IK-CAPE KVPO

503 NIST ThermoML KVTMLPO

polynomial

Stiel-Thodos

The Stiel-Thodos equation is:

Where:

Cpi*,ig is obtained from the Ideal Gas Heat Capacity model.

R is the universal gas constant.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

MW Mi — — 1.0 5000.0 —

The DIPPR equation for vapor thermal conductivity is:

(Other DIPPR equations may sometimes be used. See Pure Component

Temperature-Dependent Properties for details.)

The DIPPR equation is used in PCES when estimating vapor thermal

conductivity.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

KVDIP/1 C1i — x — — THERMAL

CONDUCTIVITY

KVDIP/2 C2i 0 x — — —

KVDIP/3, 4 C3i, C4i 0 x — — TEMPERATURE †

KVDIP/5 — 0 x — — —

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

KVDIP/6 C6i 0 x — — TEMPERATURE

KVDIP/7 C7i 1000 x — — TEMPERATURE

† If any of C2i through C4i are non-zero, absolute temperature units are

assumed for C1i through C4i. Otherwise, all coefficients are interpreted in user

input temperature units. The temperature limits are always interpreted in

user input units.

PPDS

The equation is:

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

KVPDS/1 C1i — — — — THERMAL-

CONDUCTIVITY

KVPDS/2 C2i 0 — — — THERMAL-

CONDUCTIVITY

KVPDS/3 C3i 0 — — — THERMAL-

CONDUCTIVITY

KVPDS/4 C4i 0 — — — THERMAL-

CONDUCTIVITY

KVPDS/5 C5i 0 — — — TEMPERATURE

KVPDS/6 C6i 1000 — — — TEMPERATURE

IK-CAPE Polynomial

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

KVPO/1 C1i — x — — THERMAL-

CONDUCTIVITY

KVPO/2, ... , 10 C2i, ..., C10i 0 x — — THERMAL-

CONDUCTIVITY,

TEMPERATURE

KVPO/11 C11i 0 x — — TEMPERATURE

KVPO/12 C12i 1000 x — — TEMPERATURE

NIST ThermoML Polynomial

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

KVTMLPO/1 C1i — x — — THERMAL-

CONDUCTIVITY,

TEMPERATURE

KVTMLPO/2, ... , C2i, ..., C4i 0 x — — THERMAL-

4 CONDUCTIVITY,

TEMPERATURE

KVTMLPO/5 nTerms 4 x — — —

KVTMLPO/6 Tlower 0 x — — TEMPERATURE

KVTMLPO/7 Tupper 1000 x — — TEMPERATURE

References

R.C. Reid, J.M. Praunitz, and B.E. Poling, The Properties of Gases and Liquid,

4th ed., (New York: McGraw-Hill, 1987), p. 494.

The pressure correction to a pure component or mixture thermal conductivity

at low pressure is given by:

Where:

ρrm =

Conductivity model (Stiel-Thodos/DIPPR).

This model should not be used for polar substances, hydrogen, or helium.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

MW Mi — — 1.0 5000.0 —

TC Tci — — 5.0 2000.0 TEMPERATURE

5 8

PC — — — 10 10 PRESSURE

VC Vci — — 0.001 3.5 MOLE-VOLUME

ZC Zci — — 0.1 0.5 —

References

R.C. Reid, J.M. Praunitz, and B.E. Poling, The Properties of Gases and Liquids,

4th ed., (New York: McGraw-Hill, 1987), p. 521.

Liquid mixture thermal conductivity is calculated using the Vredeveld equation

(Reid et al., 1977):

Where:

wi = Liquid phase weight fraction of component i

If option code 1 is Then n is determined by

0 (default) Option code 2, always

1

Option code 2, unless . In this case n is

set to 1.

0 (default) -2

1 0.4

2 1 (This uses a weighted average of liquid thermal

conductivities.)

For most systems, the ratio of maximum to minimum pure component liquid

thermal conductivity is between 1 and 2, where the exponent -2 is

recommended, and is the default value used.

equations:

• Sato-Riedel

• DIPPR

• IK-CAPE

See the Sato-Riedel/DIPPR/IK-CAPE model for descriptions.

Reference: R.C. Reid, J.M. Prausnitz, and T.K. Sherwood, The Properties of

Gases and Liquids, 4th ed., (New York: McGraw-Hill, 1977), p. 533.

The general form for the TRAPP thermal conductivity model is:

Where:

= Mole fraction vector

*,ig

Cpi = Ideal gas heat capacity calculated using the Aspen

Physical Property System or DIPPR ideal gas heat

capacity equations

fcn = Corresponding states correlation based on the

model for vapor and liquid thermal conductivity

made by the National Bureau of standards (NBS,

currently NIST)

The model can be used for both pure components and mixtures. The model

should be used for nonpolar components only.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

MW Mi — — 1.0 5000.0 —

TCTRAP Tci TC x 5.0 2000.0 TEMPERATURE

5 8

PCTRAP pci PC x 10 10 PRESSURE

VCTRAP Vci VC x 0.001 3.5 MOLE-VOLUME

ZCTRAP Zci ZC x 0.1 1.0 —

OMGRAP ωi OMEGA x -0.5 3.0 —

References

J.F. Ely and H.J. M. Hanley, "Prediction of Transport Properties. 2. Thermal

Conductivity of Pure Fluids and Mixtures," Ind. Eng. Chem. Fundam., Vol. 22,

(1983), pp. 90–97.

The vapor mixture thermal conductivity at low pressures is calculated from

the pure component values, using the Wassiljewa-Mason-Saxena equation:

Where:

thermal conductivity model (Stiel-Thodos/DIPPR)

model

You must supply parameters for ηi*,v(p = 0) and λi*,v.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

MW Mi — — 1.0 5000.0 —

References

R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and

Liquids, 4th ed., (New York: McGraw-Hill, 1987), pp. 530–531.

Diffusivity Models

The Aspen Physical Property System has seven built-in diffusivity models. This

section describes the diffusivity models available.

Model Type

Chapman-Enskog-Wilke-Lee (Binary) Low pressure vapor

Chapman-Enskog-Wilke-Lee (Mixture) Low pressure vapor

Dawson-Khoury-Kobayashi (Binary) Vapor

Dawson-Khoury-Kobayashi (Mixture) Vapor

Nernst-Hartley Electrolyte

Wilke-Chang (Binary) Liquid

Wilke-Chang (Mixture) Liquid

Chapman-Enskog-Wilke-Lee (Binary)

The binary diffusion coefficient at low pressures is calculated using

the Chapman-Enskog-Wilke-Lee model:

Where:

ΩD =

σij =

εij =

Lennard-Jones potential parameters for ε/k (energy parameter ) and σ

(collision diameter). To calculate δ, the dipole moment p, and either the

Stockmayer parameters or Tb and Vb are needed.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

MW Mi — — 1.0 5000.0 —

-24

MUP pi — — 0.0 5x10 DIPOLEMOMENT

TB Tbi — — 4.0 2000.0 TEMPERATURE

VB Vb — — 0.001 3.5 MOLE-VOLUME

OMEGA ωi — — -0.5 2.0 —

References

R.C. Reid, J.M. Praunitz, and B.E. Poling, The Properties of Gases and Liquids,

4th ed., (New York: McGraw-Hill, 1987), p. 587.

Chapman-Enskog-Wilke-Lee (Mixture)

The diffusion coefficient of a gas into a gas mixture at low pressures is

calculated using an equation of Bird, Stewart, and Lightfoot by default (option

code 0):

the Chapman-Enskog-Wilke-Lee model. (See Chapman-Enskog-Wilke-Lee

(Binary).)

You must provide parameters for this model.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

DVBLNC — 1 x — — —

component.

References

R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and

Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 597.

Dawson-Khoury-Kobayashi (Binary)

The binary diffusion coefficient Dijv at high pressures is calculated from the

Dawson-Khoury-Kobayashi model:

Chapman-Enskog-Wilke-Lee model.

The parameters ρmv and Vmv are obtained from the Redlich-Kwong equation-

of-state model.

You must supply parameters for these two models.

Subscript i denotes a diffusing component. j denotes a solvent.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

VC Vci — x 0.001 3.5 MOLE-VOLUME

References

R.C. Reid, J.M. Prausnitz, and T.K. Sherwood. The Properties of Gases and

Liquids, 3rd ed., (New York: McGraw-Hill, 1977), pp. 560-565.

Dawson-Khoury-Kobayashi (Mixture)

The diffusion coefficient of a gas into a gas mixture at high pressure is

calculated using an equation of Bird, Stewart, and Lightfoot by default (option

code 0):

If the first option code is set to 1, Blanc's law is used instead:

The binary diffusion coefficient Dijv at high pressures is calculated from the

Dawson-Khoury-Kobayashi model. (See Dawson-Khoury-Kobayashi (Binary).)

At low pressures (up to 1 atm) the binary diffusion coefficient is instead

calculated by the Chapman-Enskog-Wilke-Lee (Binary) model.

You must provide parameters for this model.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

DVBLNC — 1 — — — —

component.

References

R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and

Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 597.

Nernst-Hartley

The effective diffusivity of an ion i in a liquid mixture with electrolytes can be

calculated using the Nernst-Hartley model:

(1)

Where:

F = 9.65x107C/kmole (Faraday's number)

xk = Mole fraction of any molecular species k

zi = Charge number of species i

The binary diffusion coefficient of the ion with respect to a molecular species

is set equal to the effective diffusivity of the ion in the liquid mixture:

(2)

The binary diffusion coefficient of an ion i with respect to an ion j is set to the

mean of the effective diffusivities of the two ions:

The diffusivity for molecular species is calculated by the Wilke-Chang

(Mixture) model.

Parameter Symbol Default Lower Upper Units

Name/Element Limit Limit

CHARGE z 0.0 — — —

IONMOB/1 l1 —† — — AREA, MOLES

IONMOB/2 l2 0.0 — — AREA, MOLES,

TEMPERATURE

of 5.0 and issues a warning. This parameter should be specified for ions, and

not allowed to default to this value.

References

A. L. Horvath, Handbook of Aqueous Electrolyte Solutions, (Chichester: Ellis

Horwood, Ltd, 1985).

Wilke-Chang (Binary)

The Wilke-Chang model calculates the liquid diffusion coefficient of

component i in a mixture at finite concentrations:

Dijl = Djil

The equation for the Wilke-Chang model at infinite dilution is:

for methanol, 1.50 for ethanol, 1.20 for propyl

alchohols and n-butanol, and 1.00 for all other

solvents.

Vbi = Liquid molar volume at Tb of solvent i

from the Andrade/DIPPR model. You must provide

parameters for one of these models.

components

x i, x j = Apparent binary mole fractions. If the actual mole

Name/Element Limit Limit

MW Mj — 1.0 5000.0 —

VB Vbi*,l — 0.001 3.5 MOLE-VOLUME

References

R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and

Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 598–600.

Wilke-Chang (Mixture)

The Wilke-Chang model calculates the liquid diffusion coefficient of

component i in a mixture.

The equation for the Wilke-Chang model is:

With:

Where:

methanol, 1.50 for ethanol, 1.20 for propyl alchohols

and n-butanol, and 1.00 for all other solvents.

nl = Mixture liquid viscosity of all nondiffusing

components. This can be obtained from the

Andrade/DIPPR or another liquid mixture viscosity

model. You must provide parameters for one of

these models.

The parameter DLWC specifies which components diffuse. It is set to 1 for a

diffusing component and 0 for a non-diffusing component.

Parameter Symbol Default Lower Upper Units

Name/Element Limit Limit

MW Mj — 1.0 5000.0 —

Parameter Symbol Default Lower Upper Units

Name/Element Limit Limit

VB Vbi*,l — 0.001 3.5 MOLE-VOLUME

DLWC — 1 — — —

References

R.C. Reid, J.M. Praunsnitz, and B.E. Poling, The Properties of Gases and

Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 618.

The Aspen Physical Property System has the following built-in surface tension

models.This section describes the surface tension models available.

Model Type

Liquid Mixture Surface Tension Liquid-vapor

API Liquid-vapor

IAPS Water-stream

Hakim-Steinberg-Stiel/DIPPR/IK-CAPE Liquid-vapor

Onsager-Samaras Electrolyte Correction Electrolyte liquid-vapor

Modified MacLeod-Sugden Liquid-vapor

The liquid mixture surface tension is calculated using a general weighted

average expression (R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties

of Gases and Liquids, 4th. ed., New York: McGraw-Hill, 1987, p. 643):

Where:

x = Mole fraction

r = Exponent (specified by the option code)

Hadden (S. T. Hadden, Hydrocarbon Process Petrol Refiner, 45(10), 1966, p.

161) suggested that the exponent value r =1 should be used for most

hydrocarbon mixtures. However, Reid recommended the value of r in the

range of -1 to -3. The exponent value r can be specified using the model’s

Option Code (option code = 1, -1, -2, ..., -9 corresponding to the value of r).

The default value of r for this model is 1.

The pure component liquid surface tension σi*,l can be calculated by these

models:

• Hakim-Steinberg-Stiel

• DIPPR

• IK-CAPE

API Surface Tension

The liquid mixture surface tension for hydrocarbons is calculated using the

API model. This model is recommended for petroleum and petrochemical

applications. It is used in the CHAO-SEA, GRAYSON, LK-PLOCK, PENG-ROB,

and RK-SOAVE option sets. The general form of the model is:

Where:

fcn = A correlation based on API Procedure 10A32 (API Technical Data

Book, Petroleum Refining, 4th edition)

Name/Element Limit Limit

TB Tbi — — 4.0 2000.0 TEMPERATURE

SG SG — — 0.1 2.0 —

TC Tci — — 5.0 2000 TEMPERATURE

The IAPS surface tension model was developed by the International

Association for Properties of Steam. It calculates liquid surface tension for

water and steam. This model is used in option sets STEAMNBS and STEAM-

TA.

The general form of the equation for the IAPS surface tension model is:

σw=fcn(T, p)

Where:

fcn = Correlation developed by IAPS

The model is only applicable to water. No parameters are required.

Hakim-Steinberg-Stiel/DIPPR/PPDS/IK-

CAPE Liquid Surface Tension

The Aspen Physical Property System has several submodels for calculating

liquid surface tension. It uses parameter TRNSWT/5 to determine which

submodel is used. See Pure Component Temperature-Dependent Properties

for details.

If TRNSWT/5 is This equation is used And this parameter is

used

0 Hakim-Steinberg-Stiel —

106 DIPPR SIGDIP

If TRNSWT/5 is This equation is used And this parameter is

used

301 PPDS SIGPDS

401 IK-CAPE polynomial SIGPO

equation

505 NIST TDE Watson SIGTDEW

equation

511 NIST TDE expansion SIGISTE

512 NIST PPDS14 Equation SIGPDS14

Hakim-Steinberg-Stiel

The Hakim-Steinberg-Stiel equation is:

Where:

Qpi =

mi =

Parameter Symbol Default Lower Upper Units

Name/Element Limit Limit

TC Tci — 5.0 2000.0 TEMPERATURE

PC pci — PRESSURE

CHI χi 0 — — —

The DIPPR equation for liquid surface tension is:

Where:

Tri = T / Tci

(Other DIPPR equations may sometimes be used. See Pure Component

Temperature-Dependent Properties for details.)

The DIPPR model is used by PCES when estimating liquid surface tension.

temperature units.

Parameter Symbol Default Lower Upper Units

Name/Element Limit Limit

SIGDIP/1 C1i — — — SURFACE-

TENSION

SIGDIP/2, ..., 5 C2i, ..., C5i 0 — — —

SIGDIP/6 C6i 0 — — TEMPERATURE

SIGDIP/7 C7i 1000 — — TEMPERATURE

PPDS

The equation is:

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

SIGPDS/1 C1i — — — — SURFACE-

TENSION

SIGPDS/2 C2i 0 — — — —

SIGPDS/3 C3i 0 — — — —

SIGPDS/4 C4i 0 — — — TEMPERATURE

SIGPDS/5 C5i 1000 — — — TEMPERATURE

This equation is the same as the PPDS equation above, but it uses its own

parameter set which includes critical temperature.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

SIGPDS14/1 C1i — x — — N/m

SIGPDS14/2 C2i 0 x — — —

SIGPDS14/3 C3i 0 x — — —

SIGPDS14/4 Tci — x — — TEMPERATURE

SIGPDS14/5 C4i 0 x — — TEMPERATURE

SIGPDS14/6 C5i 1000 x — — TEMPERATURE

IK-CAPE Polynomial

The IK-CAPE equation is:

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

SIGPO/1 C1i — x — — SURFACE-

TENSION

SIGPO/2, ..., 10 C2i, ..., C10i 0 x — — SURFACE-

TENSION

TEMPERATURE

SIGPO/11 C11i 0 x — — TEMPERATURE

SIGPO/12 C12i 1000 x — — TEMPERATURE

This equation can be used when parameter SIGTDEW is available.

Name/Element Limit Limit

SIGTDEW/1 C1i — x — — —

SIGTDEW/2, 3, 4 C2i, C3i, C4i 0 x — — —

SIGTDEW/5 Tc — x — — TEMPERATURE

SIGTDEW/6 nTerms 4 x — — —

SIGTDEW/7 Tlower 0 x — — TEMPERATURE

SIGTDEW/8 Tupper 1000 x — — TEMPERATURE

This equation can be used when parameter SIGISTE is available.

Name/Element Limit Limit

SIGISTE/1 C1i — x — — N/m

SIGISTE/2, 3, 4 C2i, C3i, C4i 0 x — — N/m

SIGISTE/5 Tci — x — — TEMPERATURE

SIGISTE/6 nTerms 4 x — — —

SIGISTE/7 Tlower 0 x — — TEMPERATURE

SIGISTE/8 Tupper 1000 x — — TEMPERATURE

References

R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and

Liquids, 4th. ed., (New York: McGraw-Hill, 1987), p. 638.

Onsager-Samaras

The Onsager-Samaras model calculates the correction to the liquid mixture

surface tension of a solvent mixture, due to the presence of electrolytes:

for salt concentration < 0.03 (1)

M

Where:

by the Hakim-Steinberg-Stiel model

xcaa = Mole fraction of the apparent electrolyte ca

to apparent electrolyte ca

For each apparent electrolyte ca, the contribution to the surface tension

correction is calculated as:

(2)

Where:

ccaa =

model

Apparent electrolyte mole fractions are computed from the true ion mole-

fractions and ionic charge number. They are also computed if you use the

apparent component approach. See Apparent Component and True

Component Approaches in the Electrolyte Calculation chapter for a more

detailed discussion of this method.

Above salt concentration 0.03 M, the slope of surface tension vs. mole

fraction is taken to be constant at the value from 0.03 M.

You must provide parameters for the Hakim-Steinberg-Stiel model, used for

the calculation of the surface tension of the solvent mixture.

Parameter Symbol Default Lower Upper Units

Name/Element Limit Limit

CHARGE z 0.0 — — —

References

A. L. Horvath, Handbook of Aqueous Electrolyte Solutions, (Chichester: Ellis,

Ltd. 1985).

Modified MacLeod-Sugden

The modified MacLeod-Sugden equation for mixture liquid surface tension can

be derived from the standard MacLeod-Sugden equation by assuming that the

density of the vapor phase is zero. The modified MacLeod-Sugden equation is:

Where:

the Hakim-Steinberg-Stiel/DIPPR/IK-CAPE model.

Vi*,l = Liquid molar volume for pure component i, calculated

using the Rackett/DIPPR/IK-CAPE model.

l

V = Mixture liquid molar volume, calculated using the

Rackett model.

References

R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and

Liquids, 3rd. ed., (New York: McGraw-Hill, 1977).

4 Nonconventional Solid

Property Models

This section describes the nonconventional solid density and enthalpy models

available in the Aspen Physical Property System. The following table lists the

available models and their model names. Nonconventional components are

solid components that cannot be characterized by a molecular formula. These

components are treated as pure components, though they are complex

mixtures.

General Enthalpy and Model name Phase(s)

Density Models

General density polynomial DNSTYGEN S

General heat capacity ENTHGEN S

polynomial

Enthalpy and Density Model name Phase(s)

Models for Coal and Char

General coal enthalpy model HCOALGEN S

IGT coal density model DCOALIGT S

IGT char density model DCHARIGT S

Models

The Aspen Physical Property System has two built-in general enthalpy and

density models. This section describes the general enthalpy and density

models available:

General Density Polynomial

DNSTYGEN is a general model that gives the density of any nonconventional

solid component. It uses a simple mass fraction weighted average for the

reciprocal temperature-dependent specific densities of its individual

constituents. There may be up to twenty constituents with mass percentages.

You must define these constituents, using the general component attribute

GENANAL. The equations are:

Where:

wij = Mass fraction of the jth constituent in component i

Name/Element Limit Limit

DENGEN/1, 5, 9, …, 77 ai,j1 x — — — MASS-ENTHALPY

and TEMPERATURE

DENGEN/2, 6, 10, …, ai,j2 x 0 — — MASS-ENTHALPY

78 and TEMPERATURE

DENGEN/3, 7, 11, …, ai,j3 x 0 — — MASS-ENTHALPY

79 and TEMPERATURE

DENGEN/4, 8, 12, …, ai,j4 x 0 — — MASS-ENTHALPY

80 and TEMPERATURE

constituents. The structure of DENGEN is: Elements 1 to 4 are the four

coefficients for the first constituent, elements 5 to 8 are the coefficients for

the second constitutent, and so on, for up to 20 constituents.

ENTHGEN is a general model that gives the specific enthalpy of any

nonconventional component as a simple mass-fraction-weighted-average for

the enthalpies of its individual constituents. You may define up to twenty

constituents with mass percentages, using the general component attribute

GENANAL. The specific enthalpy of each constituent at any temperature is

calculated by combining specific enthalpy of formation of the solid with a

sensible heat change. (See Nonconventional Component Enthalpy Calculation

in Physical Property Methods.)

The equations are:

Where:

wij = Mass fraction of the jth constituent in

component i

hi s = Specific enthalpy of solid component i

component i

Name/Element Limit Limit

DHFGEN/J Δfhjs x 0 — — MASS-ENTHALPY

and

TEMPERATURE

HCGEN/2, 6, 10, …, 78 ai,j2 x 0 — — MASS-ENTHALPY

and

TEMPERATURE

HCGEN/3, 7, 11, …, 79 ai,j3 x 0 — — MASS-ENTHALPY

and

TEMPERATURE

HCGEN/4, 8, 12, …, 80 ai,j4 x 0 — — MASS-ENTHALPY

and

TEMPERATURE

The elements of GENANAL are used to input the mass percentages of the

constituents. The structure for HCGEN is: Elements 1 to 4 are the four

coefficients for the first constituent, elements 5 to 8 are the coefficients for

the second constitutent, and so on, for up to 20 constituents.

for Coal and Char

Coal is modeled in the Aspen Physical Property System as a nonconventional

solid. Coal models are empirical correlations, which require solid material

characterization information. Component attributes are derived from

constituent analyses. Definitions of coal component attributes are given in the

Aspen Plus User Guide, Chapter 6.

Enthalpy and density are the only properties calculated for nonconventional

solids. This section describes the special models available in the Aspen

Physical Property System for the enthalpy and density of coal and char. The

component attributes required by each model are included. The coal models

are:

• General coal enthalpy

• IGT Coal Density

• IGT Char Density

• User models for density and enthalpy. See User Models for

Nonconventional Properties in Chapter 6 of Aspen Plus User Models, for

details on writing the subroutines for these user models.

Notation

Most correlations for the calculation of coal properties require proximate,

ultimate, and other analyses. These are converted to a dry, mineral-matter-

free basis. Only the organic portion of the coal is considered.

Moisture corrections are made for all analyses except hydrogen, according to

the formula:

Where:

w = The value determined for weight fraction

d

w = The value on a dry basis

= The moisture weight fraction

The mineral matter content is calculated using the modified Parr formula:

The ash term corrects for water lost by decomposition of clays in the ash

determination. The average water constitution of clays is assumed to be 11.2

percent. The sulfur term allows for loss in weight of pyritic sulfur when pyrite

is burned to ferric oxide. The original Parr formula assumed that all sulfur is

pyritic sulfur. This formula included sulfatic and organic sulfur in the mineral-

matter calculation. When information regarding the forms of sulfur is

available, use the modified Parr formula to give a better approximation of the

percent of inorganic material present. Because chlorine is usually small for

United States coals, you can omit chlorine from the calculation.

Correct analyses from a dry basis to a dry, mineral-matter-free basis, using

the formula:

Where:

Δwd = Correction factor for other losses, such as the loss

of carbon in carbonates and the loss of hydrogen

present in the water constitution of clays

The oxygen and organic sulfur contents are usually calculated by difference

as:

Where:

Cp = Heat capacity / (J/kgK)

cp = Heat capacity / (cal/gC)

h = Specific enthalpy

T = Temperature/K

t = Temperature/C

w = Weight fraction

ρ = Specific density

Subscripts:

A = Ash

C = Carbon

Cl = Chlorine

FC = Fixed carbon

H = Hydrogen

H2O = Moisture

MM = Mineral matter

N = Nitrogen

O = Oxygen

So = Organic sulfur

Sp = Pyritic sulfur

St = Total sulfur

S = Other sulfur

VM = Volatile matter

Superscripts:

d = Dry basis

m = Mineral-matter-free basis

The general coal model for computing enthalpy in the Aspen Physical Property

System is HCOALGEN. This model includes a number of different correlations

for the following:

• Heat of combustion

• Heat of formation

• Heat capacity

You can select one of these correlations using an option code in the Properties

Advanced NC-Props form. (See the Aspen Plus User Guide, Chapter 6). Use

option codes to specify a calculation method for properties. Each element in

the option code vector is used in the calculation of a different property.

The table labeled HCOALGEN Option Codes (below) lists model option codes

for HCOALGEN. The table is followed by a detailed description of the

calculations used for each correlation.

The correlations are described in the following section. The component

attributes are defined in Aspen Plus User Guide, Chapter 6.

The heat of combustion of coal in the HCOALGEN model is a gross calorific

value. It is expressed in Btu/lb of coal on a dry mineral-matter-free basis.

ASTM Standard D-2015 defines standard conditions for measuring gross

calorific value. Initial oxygen pressure is 20 to 40 atmospheres. Products are

in the form of ash; liquid water; and gaseous CO2, SO2, and NO2.

You can calculate net calorific value from gross calorific value by making a

deduction for the latent heat of vaporization of water.

Heat of combustion values are converted back to a dry, mineral-matter-

containing basis with a correction for the heat of combustion of pyrite. The

formula is:

Technology (IGT). They used data for 121 samples of coal from the Penn

State Data Base (IGT, 1976) and 457 samples from a USGS report (Swanson,

et al., 1976). These samples included a wide range of United States coal

fields. The constant terms in the HCOALGEN correlations are bias corrections

obtained from the IGT study.

Boie Correlation:

BOIEC/1 a1i 151.2

BOIEC/2 a2i 499.77

BOIEC/3 a3i 45.0

BOIEC/4 a4i -47.7

BOIEC/5 a5i 27.0

BOIEC/6 a6i -189.0

Dulong Correlation:

DLNGC/1 a1i 145.44

DLNGC/2 a2i 620.28

DLNGC/3 a3i 40.5

DLNGC/4 a4i -77.54

DLNGC/5 a5i -16.0

GMLDC/1 a1i 0.3333

GMLDC/2 a2i 654.3

GMLDC/3 a3i 0.125

GMLDC/4 a4i 0.125

GMLDC/5 a5i 424.62

GMLDC/6 a6i -2.0

MTSPC/1 a1i 144.54

MTSPC/2 a2i 610.2

MTSPC/3 a3i 40.3

MTSPC/4 a4i 62.45

MTSPC/5 a5i 30.96

MTSPC/6 a6i 65.88

Parameter Name/Element Symbol Default

MTSPC/7 a7i -47.0

IGT Correlation:

CIGTC/1 a1i 178.11

CIGTC/2 a2i 620.31

CIGTC/3 a3i 80.93

CIGTC/4 a4i 44.95

CIGTC/5 a5i -5153.0

Parameter Name/Element Symbol Default

HCOMB Δchid 0

There are two standard heat of formation correlations for the HCOALGEN

model:

• Heat of combustion-based

• Direct

Heat of Combustion-Based Correlation This is based on the assumption that

combustion results in complete oxidation of all elements except sulfatic sulfur

and ash, which are considered inert. The numerical coefficients are

combinations of stoichiometric coefficients and heat of formation for CO2,

H2O, HCl, and NO2 at 298.15K:

of 1% in the heat of a combustion-based correlation produces about a 50%

error when it is used to calculate the heat of formation. For this reason, the

following direct correlation was developed, using data from the Penn State

Data Base. It has a standard deviation of 112.5 Btu/lb, which is close to the

limit, due to measurement in the heat of combustion:

Where:

Parameter Name/Element Symbol Default

HFC/1 a1i 1810.123

HFC/2 a2i -502.222

HFC/3 a3i 329.1087

HFC/4 a4i 121.766

HFC/5 a5i -542.393

HFC/6 a6i 1601.573

HFC/7 a7i 424.25

HFC/8 a8i -525.199

HFC/9 a9i -11.4805

HFC/10 a10i 31.585

HFC/11 a11i 13.5256

HFC/12 a12i 11.5

HFC/13 a13i -685.846

HFC/14 a14i -22.494

HFC/15 a15i -64836.19

The Kirov correlation (1965) considered coal to be a mixture of moisture, ash,

fixed carbon, and primary and secondary volatile matter. Secondary volatile

matter is any volatile matter up to 10% on a dry, ash-free basis; the

remaining volatile matter is primary. The correlation developed by Kirov

treats the heat capacity as a weighted sum of the heat capacities of the

constituents:

Where:

i = Component index

j = Constituent index j = 1, 2 , ... , ncn

Where the values of j represent:

1 Moisture

2 Fixed carbon

3 Primary volatile matter

4 Secondary volatile matter

5 Ash

wj = Mass fraction of jth constituent on dry basis

This correlation calculates heat capacity in cal/gram-C using temperature in

C. The parameters must be specified in appropriate units for this conversion.

Parameter Name/Element Symbol Default

CP1C/1 ai,11 1.0

CP1C/2 ai,12 0

CP1C/3 ai,13 0

CP1C/4 ai,14 0

CP1C/5 ai,21 0.165

CP1C/6 ai,22

CP1C/7 ai,23

CP1C/8 ai,24 0

CP1C/9 ai,31 0.395

CP1C/10 ai,32

CP1C/11 ai,33 0

CP1C/12 ai,34 0

CP1C/13 ai,41 0.71

CP1C/14 ai,42

CP1C/15 ai,43 0

CP1C/16 ai,44 0

CP1C/17 ai,51 0.18

CP1C/18 ai,52

CP1C/19 ai,53 0

CP1C/20 ai,54 0

The cubic temperature equation is:

CP2C/1 a1i 0.438

CP2C/2 a2i

CP2C/3 a3i

CP2C/4 a4i

The default values of the parameters were developed by Gomez, Gayle, and

Taylor (1965). They used selected data from three lignites and a

subbituminous B coal, over a temperature range from 32.7 to 176.8°C.

Option Code Option Code Calculation Parameter Component

Number Value† Method Names Attributes

1 Heat of Combustion

1 Boie correlation BOIEC ULTANAL

SULFANAL

PROXANAL

Option Code Option Code Calculation Parameter Component

Number Value† Method Names Attributes

1 Heat of Combustion

2 Dulong DLNGC ULTANAL

correlation SULFANAL

PROXANAL

3 Grummel and GMLDC ULTANAL

Davis correlation SULFANAL

PROXANAL

4 Mott and Spooner MTSPC ULTANAL

correlation SULFANAL

PROXANAL

5 IGT correlation CIGTC ULTANAL

PROXANAL

6 User input value HCOMB ULTANAL

PROXANAL

2 Standard Heat of Formation

1 Heat-of- — ULTANAL

combustion- SULFANAL

based correlation

2 Direct correlation HFC ULTANAL

SULFANAL

PROXANAL

3 Heat Capacity

1 Kirov correlation CP1C PROXANAL

2 Cubic CP2C —

temperature

equation

4 Enthalpy Basis

1 Elements in their — —

standard states — —

at 298.15K and 1

atm

2 Component at — —

298.15 K

†

Default = 1 for each option code

References

Gomez, M., J.B. Gayle, and A.R. Taylor, Jr., Heat Content and Specific Heat of

Coals and Related Products, U.S. Bureau of Mines, R.I. 6607, 1965.

IGT (Institute of Gas Technology), Coal Conversion Systems Technical Data

Book, Section PMa. 44.1, 1976.

Kirov, N.Y., "Specific Heats and Total Heat Contents of Coals and Related

Materials are Elevated Temperatures," BCURA Monthly Bulletin, (1965),

pp. 29, 33.

Swanson, V.E. et al., Collection, Chemical Analysis and Evaluation of Coal

Samples in 1975, U.S. Geological Survey, Open-File Report (1976), pp. 76–

468.

IGT Coal Density Model

The DCOALIGT model gives the true (skeletal or solid-phase) density of coal

on a dry basis. It uses ultimate and sulfur analyses. The model is based on

equations from IGT (1976):

The equation for ρidm is good for a wide range of hydrogen contents, including

anthracities and high temperature cokes. The standard deviation of this

correlation for a set of 190 points collected by IGT from the literature was

12x10-6 m3/kg. The points are essentially uniform over the whole range. This

is equivalent to a standard deviation of about 1.6% for a coal having a

hydrogen content of 5%. It increases to about 2.2% for a coke or anthracite

having a hydrogen content of 1%.

Parameter Name/Element Symbol Default

DENIGT/1 a1i 0.4397

DENIGT/2 a2i 0.1223

DENIGT/3 a3i -0.01715

DENIGT/4 a4i 0.001077

Reference

IGT (Institute of Gas Technology), Coal Conversion Systems Technical Data

Book, Section PMa. 44.1, 1976.

The DGHARIGT model gives the true (skeletal or solid-phase) density of char

or coke on a dry basis. It uses ultimate and sulfur analyses. This model is

based on equations from IGT (1976):

Parameter Name/Element Symbol Default

DENIGT/1 a1i 0.4397

DENIGT/2 a2i 0.1223

DENIGT/3 a3i -0.01715

DENIGT/4 a4i 0.001077

from 2.2x103 to 2.26x103 kg/m3. Densities of nongraphitic high-temperature

carbons (derived from chars) range from 2.0x103 to 2.2x103 kg/m3. Most of

the data used in developing this correlation were for carbonized coking coals.

Although data on a few chars (carbonized non-coking coals) were included,

none has a hydrogen content less than 2%. The correlation is probably not

accurate for high temperature chars.

References

I.M. Chang, B.S. Thesis, Massachusetts Institute of Technology, 1979.

M. Gomez, J.B. Gayle, and A.R. Taylor, Jr., Heat Content and Specific Heat of

Coals and Related Products, U.S. Bureau of Mines, R.I. 6607, 1965.

IGT (Institute of Gas Technology), Coal Conversion Systems Technical Data

Book, Section PMa. 44.1, 1976.

N.Y. Kirov, "Specific Heats and Total Heat Contents of Coals and Related

Materials are Elevated Temperatures," BCURA Monthly Bulletin, (1965),

pp. 29, 33.

V.E. Swanson et al., Collection, Chemical Analysis and Evaluation of Coal

Samples in 1975, U.S. Geological Survey, Open-File Report (1976), pp. 76–

468.

5 Property Model Option

Codes

• Option Codes for Transport Property Models

• Option Codes for Activity Coefficient Models

• Option Codes for Equation of State Models

• Option Codes for K-value Models

• Option Codes for Enthalpy Models

• Option Codes for Gibbs Energy Models

• Option Codes for Molar Volume Models

Property Models

Model Name Option Value Descriptions

Code

SIG2HSS 1 1 Exponent in mixing rule (default)

-1,-2, Exponent in mixing rule

..., -9

SIG2ONSG 1 1 Exponent in mixing rule (default)

-1,-2, Exponent in mixing rule

..., -9

MUL2API, 1 0 Release 9 method. First, the API, SG of the

MULAPI92 mixture is calculated, then the API correlation is

used (default)

1 Pre-release 9 method. Liquid viscosity is

calculated for each pseudocomponent using the

API method. Then mixture viscosity is

calculated by mixing rules.

MUL2ANDR, 1 0 Mixture viscosity weighted by mole fraction

DL0WCA, DL1WCA, (default)

DL0NST, DL1NST

Model Name Option Value Descriptions

Code

1 Mixture viscosity weighted by mass fraction

(default)

1 Mixture viscosity weighted by mass fraction

2 0 Use Breslau and Miller equation instead of Jones

and Dole equation when electrolyte

concentration exceeds 0.1 M.

1 Always use Jones and Dole equation when the

parameters are available.

3 0 Solvent liquid mixture viscosity from Andrade

liquid mixture viscosity model (default)

1 Solvent liquid mixture viscosity from quadratic

mixing rule

2 Solvent liquid mixture viscosity from Aspen

liquid mixture viscosity model

MUL2CLS, 1 0 Original correlation

MUL2CLS2

1 Modified UOP correlation

MUL2QUAD 1 0 Use mole basis composition (default)

1 Use mass basis composition

KL2VR, KL2RDL 1 0 Do not check ratio of KL max / KL min

exponent to 1, overriding option code 2.

2 0 Exponent is -2

1 Exponent is 0.4

2 Exponent is 1. This uses a weighted average of

liquid thermal conductivities.

Coefficient Models

Model Name Option Value Descriptions

Code

GMXSH 1 0 No volume term (default)

1 Includes volume term

WHENRY 1 1 Equal weighting

2 Size - VC1/3

3 Area - VC2/3 (default)

4 Volume - VC

Electrolyte NRTL Activity Coefficient Model (GMENRTL, GMELC, GMENRHG)

1 Defaults for pair parameters

Model Name Option Value Descriptions

Code

1 Pair parameters default to zero

2 Solvent/solute pair parameters default to water

parameters. Water/solute pair parameters

default to zero (default for GMELC)

3 Default water parameters to 8, -4. Default

solvent/solute parameters to 10, -2 (default for

GMENRTL and GMENRHG)

2 Vapor phase equation-of-state for liquid enthalpy

and Gibbs energy of HF

0 Ideal gas EOS (default)

1 HF EOS for hydrogen fluoride

3 Solvent/solvent binary parameter values

obtained from

0 Scalar GMELCA, GMELCB and GMELCM (default

for GMELC)

1 Vector NRTL(8) (default for GMENRTL and

GMENRHG)

4 Enthalpy calculation method

0 Electrolyte NRTL Enthalpy (default for GMELC)

1 Helgeson method (default for GMENRTL and

GMENRHG)

5 Vapor phase enthalpy departure contribution to

liquid enthalpy. Hliq = Hig + DHV - ΔHvap; this

option indicates how DHV is calculated.

0 Do not calculate (DHV=0) (default)

1 Calculate using Redlich-Kwong equation of state

2 Calculate using Hayden-O'Connell equation of

state

6 Method for calculating corresponding states (for

handling solvents that exist in both subcritical

and supercritical conditions)

0 Original method (default)

1 Corresponding state method. Calculates a

pseudo-critical temperature of the solvents and

uses it together with the actual critical

temperatures of the pure solvents to adjust the

liquid enthalpy departure. This results in a

smoother transition of the liquid enthalpy

contribution when the component transforms

from subcritical to supercritical.

GMPT1 1 Defaults for pair mixing rule

-1 No unsymmetric mixing

0 Unsymmetric mixing polynomial (default)

1 Unsymmetric mixing integral

GAQPT3, GMPT3, 1 Defaults for pair mixing rule

HAQPT3 -1 No unsymmetric mixing

0 Unsymmetric mixing polynomial (default)

Model Name Option Value Descriptions

Code

1 Unsymmetric mixing integral

2 Standard enthalpy calculation

0 Standard electrolytes method (Pre-release 10)

1 Helgeson method (Default)

3 Estimation of K-stoic temperature dependency

0 Use value at 298.15 K

1 Helgeson Method (default)

1 Reference temperature usage

COSMOSAC

1 Model choice

1 COSMO-SAC model by Lin and Sandler (2002)

(Default)

2 COSMO-RS model by Klamt and Eckert (2000)

3 Lin and Sandler model with modified exchange

energy (Lin et al., 2002)

HS0POL1, GS0POL1, SS0POL1 (Solid pure component polynomials)

1 0 Use standard reference temperature (default)

1 Use liquid reference temperature

Hansen

1 0 Hansen volume input by user (default)

1 Hansen volume calculated by Aspen Plus

NRTL-SAC (patent pending), ENRTL-SAC (patent pending)

1 0 Flory-Huggins term included (default)

1 Flory-Huggins term removed

PHILELC

1 Steam table for liquid enthalpy of water

0 Use steam table for liquid enthalpy of water

(default)

1 Use specified EOS model

2 Vapor phase equation-of-state for liquid enthalpy

of HF

0 Use specified EOS model (default)

1 HF EOS for hydrogen fluoride

State Models

Model Name Option Value Descriptions

Code

ESBWRS, ESBWRS0 1 0 Do not use steam tables

1 Calculate properties (H, S, G, V) of water from

steam table (default; see Note)

Model Name Option Value Descriptions

Code

2 0 Original RT-Opt root search method (default)

1 VPROOT/LQROOT Aspen Plus root search

method. Use this if the equation-oriented Aspen

Plus solution fails to converge and some

streams with missing phases show the same

properties for the missing phase as for another

phase.

ESHOC, ESHOC0, 1 0 Hayden-O'Connell model. Use chemical theory

PHV0HOC only if one component has HOCETA=4.5

(default)

1 Always use the chemical theory regardless of

HOCETA values

2 Never use the chemical theory regardless of

HOCETA values

2 0 Check high-pressure limit. If exceeded,

calculate volume at cut-off pressure.

1 Ignore high-pressure limit. Calculate volume

model T and P.

ESPR, ESPR0, 1 0 ASPEN Boston/Mathias alpha function when Tr

ESPRSTD, >1, original literature alpha function otherwise.

ESPRSTD0 (default for ESPR)

1 Original literature alpha function (default for

ESPRSTD)

2 Extended Gibbons-Laughton alpha function

3 Twu Generalized alpha function

4 Twu alpha function

2 0 Standard Peng-Robinson mixing rules (default)

1 Asymmetric Kij mixing rule from Dow

1 Calculate water properties (H, S, G, V) from

steam table (see Note)

4 0 Do not use Peneloux liquid volume correction

(default)

1 Apply Peneloux liquid volume correction (See

SRK)

5 0 Use analytical method for root finding (default)

1 Use RTO numerical method for root finding

root finding

ESPRWS, 1 0 ASPEN Boston/Mathias alpha function

ESPRWS0, ESPRV1,

ESPRV10, ESPRV2,

ESPRV20,

ESPSAFT, 1 0 Random copolymer (default)

ESPSAFT0

Model Name Option Value Descriptions

Code

1 Alternative copolymer

2 Block copolymer

2 0 Do not use Sadowski's copolymer model

1 Use Sadowski's copolymer model in which a

copolymer must be built only by two different

types of segments

3 0 Use association term (default)

1 Do not use association term

ESRKS, ESRKS0, See Soave-Redlich-Kwong Option Codes

ESRKSTD,

ESRKSTD0, ESSRK,

ESSRK0, ESRKSML,

ESRKSML0

ESRKSW, ESRKSW0 1 0 ASPEN Boston/Mathias alpha function (default)

1 Original literature alpha function

2 Grabowski and Daubert alpha function for H2

above TC (α = 1.202 exp(-0.30228xTri))

ESRKU, ESRKU0 1 Initial temperature for binary parameter

estimation

0 At TREF=25 C (default)

1 The lower of TB(i) or TB(j)

2 (TB(i) + TB(j))/2

>2 Value entered used as temperature

2 VLE or LLE UNIFAC

0 VLE (default)

1 LLE

3 Property diagnostic level flag (-1 to 8)

4 Vapor phase EOS used in generation of TPxy

data with UNIFAC

0 Hayden-O'Connell (default)

1 Redlich-Kwong

5 Do/do not estimate binary parameters

0 Estimate (default)

1 Set to zero

ESHF, ESHF0 1 0 Equation form for Log(k) expression:

log(K) = A + B/T + C ln(T) + DT (default)

1 log(K) = A + B/T + CT + DT2 + E log(P)

1 Original literature alpha function

2 Mathias-Copeman alpha function

3 Schwartzentruber-Renon alpha function

(default)

Model Name Option Value Descriptions

Code

ESRKSWS, 1 Equation form for alpha function

ESRKSWS0,

ESRKSV1,

ESRKSV10,

ESRKSV2,

ESRKSV20,

1 Original literature alpha function

2 Mathias-Copeman alpha function

3 Schwartzentruber-Renon alpha function

(default)

ESSTEAM, 1 0 ASME 1967 correlations

ESSTEAM0

1 NBS 1984 equation of state (default)

2 NBS 1984 equation of state with alternate root

search method (STMNBS2)

2 0 Original fugacity and enthalpy calculations

when used with STMNBS2

1 Rigorous fugacity calculation from Gibbs energy

and corrected enthalpy departure (default)

ESH2O, ESH2O0 1 0 ASME 1967 correlations (default)

1 NBS 1984 equation of state

2 NBS 1984 equation of state with alternate root

search method (STMNBS2)

Note: The enthalpy, entropy, Gibbs energy, and molar volume of water are

calculated from the steam tables when the relevant option is enabled. The

total properties are mole-fraction averages of these values with the properties

calculated by the equation of state for other components. Fugacity coefficient

is not affected.

Soave-Redlich-Kwong Option

Codes

There are five related models all based on the Soave-Redlich-Kwong equation

of state which are very flexible and have many options. These models are:

• Standard Redlich-Kwong-Soave (ESRKSTD0, ESRKSTD)

• Redlich-Kwong-Soave-Boston-Mathias (ESRKS0, ESRKS)

• Soave-Redlich-Kwong (ESSRK, ESSRK0)

• SRK-Kabadi-Danner (ESSRK, ESSRK0)

• SRK-ML (ESRKSML, ESRKSML0)

The options for these models can be selected using the option codes

described in the following table:

Option Value Description

Code

1 0 Standard SRK alpha function for Tr < 1, Boston-Mathias alpha

function for Tr > 1

1 Standard SRK alpha function for all

2 Grabovsky – Daubert alpha function for H2 and standard SRK

alpha function for others (default)

3 Extended Gibbons-Laughton alpha function for all components

(see notes 1, 2, 3)

4 Mathias alpha function

5 Twu generalized alpha function

2 0 Standard SRK mixing rules (default except for SRK-Kabadi-

Danner)

1 Kabadi – Danner mixing rules (default for SRK-Kabadi-Danner)

(see notes 3, 4, 5)

3 0 Do not calculate water properties from steam table (default for

Redlich-Kwong-Soave models)

1 Calculate properties (H, S, G, V) of water from steam table

(default for SRK models; see note 6)

4 0 Do not apply the Peneloux liquid volume correction

1 Apply the liquid volume correction (default)

5 0 Use analytical method for root finding (default)

1 Use RTO numerical method for root finding

2 Use VPROOT/LQROOT numerical method for root finding

6 0 Use true logarithm in calculating properties (default for

Redlich-Kwong-Soave models)

1 Use smoothed logarithm in calculating properties (default for

SRK models)

Notes

1. The standard alpha function is always used for Helium.

2. If extended Gibbons-Laughton alpha function parameters are missing, the

Boston-Mathias extrapolation will be used if T > Tc, and the standard

alpha function will be used if T < Tc.

3. The extended Gibbons-Laughton alpha function should not be used with

the Kabadi-Danner mixing rules.

4. The Kabadi-Danner mixing rules should not be used if Lij parameters are

provided for water with any other components.

5. It is recommended that you use the SRK-KD property method rather than

change this option code.

6. The enthalpy, entropy, Gibbs energy, and molar volume of water are

calculated from the steam tables when this option is enabled. The total

properties are mole-fraction averages of these values with the properties

calculated by the equation of state for other components. Fugacity

coefficient is not affected.

Option Codes for K-Value

Models

Model Option Value Descriptions

Name Code

BK10 1 0 Treat pseudocomponents as paraffins (default)

1 Treat pseudocomponents as aromatics

Models

Model Name Option Value Descriptions

Code

DHL0HREF 1 1 Use Liquid reference state for all components (Default)

2 Use liquid and gaseous reference states based on the

state of each component

Electrolyte NRTL Enthalpy (HMXENRTL, HAQELC, HMXELC, HMXENRHG)

1 Defaults for pair parameters

1 Pair parameters default to zero

2 Solvent/solute pair parameters default to water

parameters. Water/solute pair parameters default to

zero (default for ELC models)

3 Default water parameters to 8, -4. Default

solvent/solute parameters to 10, -2 (default for

HMXENRTL and HMXENRHG)

2 Vapor phase equation-of-state for liquid enthalpy and

Gibbs energy of HF

0 Ideal gas EOS (default)

1 HF EOS for hydrogen fluoride

3 Solvent/solvent binary parameter values obtained

from:

0 Scalar GMELCA, GMELCB and GMELCM (default for ELC

models)

1 Vector NRTL(8) (default for HMXENRTL and

HMXENRHG)

4 Enthalpy calculation method

0 Electrolyte NRTL Enthalpy (default for ELC models,

HMXENRTL, and ELECNRTL property method)

1 Helgeson method (default for HMXENRHG)

5 Vapor phase enthalpy departure contribution to liquid

enthalpy. Hliq = Hig + DHV - ΔHvap; this option indicates

how DHV is calculated.

0 Do not calculate (DHV=0) (default)

1 Calculate using Redlich-Kwong equation of state

2 Calculate using Hayden-O'Connell equation of state

Model Name Option Value Descriptions

Code

6 Method for calculating corresponding states (for

handling solvents that exist in both subcritical and

supercritical conditions)

0 Original method (default)

1 Corresponding state method. Calculates a pseudo-

critical temperature of the solvents and uses it

together with the actual critical temperatures of the

pure solvents to adjust the liquid enthalpy departure.

This results in a smoother transition of the liquid

enthalpy contribution when the component transforms

from subcritical to supercritical.

7 Method for handling Henry components and multiple

solvents

0 Pure liquid enthalpy calculated by aqueous infinite

dilution heat capacity; only water as solvent

1 Pure liquid enthalpy for Henry components calculated

using Henry's law; use this option when there are

multiple solvents.

HLRELNRT, HLRELELC

1 Defaults for pair parameters

1 Pair parameters default to zero

2 Solvent/solute pair parameters default to water

parameters. Water/solute pair parameters default to

zero (default for HLRELELC)

3 Default water parameters to 8, -4. Default

solvent/solute parameters to 10, -2 (default for

HLRENRTL)

2 Solvent/solvent binary parameter values obtained

from:

0 Scalar GMELCA, GMELCB and GMELCM (default)

1 Vector NRTL(8)

3 Mixture density model

0 Rackett equation with Campbell-Thodos modification

1 Quadratic mixing rule for molecular components (mole

basis)

HIG2ELC, HIG2HG

1 Enthalpy calculation method

0 Electrolyte NRTL Enthalpy (default for HIG2ELC)

1 Helgeson method (default for HIG2HG)

DHLELC

1 Steam table for liquid enthalpy of water

0 Use steam table for liquid enthalpy of water (default)

1 Use specified EOS model

2 Vapor phase equation-of-state for liquid enthalpy of HF

0 Use specified EOS model (default)

1 HF EOS for hydrogen fluoride

Option Codes for Gibbs Energy

Models

Model Name Option Value Descriptions

Code

Electrolyte NRTL Gibbs Energy (GMXENRTL, GAQELC, GMXELC, GMXENRHG)

1 Defaults for pair parameters

1 Pair parameters default to zero

2 Solvent/solute pair parameters default to water

parameters. Water/solute pair parameters

default to zero (default for ELC models)

3 Default water parameters to 8, -4. Default

solvent/solute parameters to 10, -2 (default for

GMXENRTL and GMXENRHG)

2 Vapor phase equation-of-state for liquid enthalpy

and Gibbs energy of HF

0 Ideal gas EOS (default)

1 HF EOS for hydrogen fluoride

3 Solvent/solvent binary parameter values

obtained from

0 Scalar GMELCA, GMELCB and GMELCM (default

for ELC models)

1 Vector NRTL(8) (default for GMXENRTL and

GMXENRHG)

4 Enthalpy calculation method

0 Electrolyte NRTL Enthalpy (default for ELC

models)

1 Helgeson method (default for GMXENRTL and

GMXENRHG)

5 Vapor phase enthalpy departure contribution to

liquid enthalpy. Hliq = Hig + DHV - ΔHvap; this

option indicates how DHV is calculated.

0 Do not calculate (DHV=0) (default)

1 Calculate using Redlich-Kwong equation of state

2 Calculate using Hayden-O'Connell equation of

state

6 Method for handling Henry components and

multiple solvents

0 Pure liquid enthalpy calculated by aqueous

infinite dilution heat capacity; only water as

solvent

1 Pure liquid enthalpy for Henry components

calculated using Henry's law; use this option

when there are multiple solvents.

GLRELNRT, GLRELELC

1 Defaults for pair parameters

1 Pair parameters default to zero

Model Name Option Value Descriptions

Code

2 Solvent/solute pair parameters default to water

parameters. Water/solute pair parameters

default to zero (default for GLRELELC)

3 Default water parameters to 8, -4. Default

solvent/solute parameters to 10, -2 (default for

GLRENRTL)

2 Solvent/solvent binary parameter values

obtained from:

0 Scalar GMELCA, GMELCB and GMELCM (default)

1 Vector NRTL(8)

3 Mixture density model

0 Rackett equation with Campbell-Thodos

modification

1 Quadratic mixing rule for molecular components

(mole basis)

GIG2ELC, GIG2HG

1 Enthalpy calculation method

0 Electrolyte NRTL Enthalpy (default for GIG2ELC)

1 Helgeson method (default for GIG2HG)

Models

Model Option Value Descriptions

Name Code

VL2QUAD 1 0 Use normal pure component liquid volume model for

all components (default)

1 Use steam tables for water

2 0 Use mole basis composition (default)

1 Use mass basis composition

VAQCLK 1 0 Use Clarke model

1 Use liquid volume quadratic mixing rule

Index

A 213

Brokaw-Wilke mixing rule

Activity coefficient models 83 viscosity model 216

list of property models 83 Wilke-Lee (binary) diffusion

Andrade/DIPPR viscosity model model 242

207 Wilke-Lee (mixture) diffusion

Antoine/Wagner vapor pressure model 243

model 147 Chien-Null activity coefficient

API 1997 Liquid Viscosity 211 model 86

API model 160, 211, 249 Chung-Lee-Starling model 218,

liquid viscosity 211 220, 230

liquid volume 160 low pressure vapor viscosity 218

surface tension 249 thermal conductivity 230

API Sour model 152 viscosity 220

Applications 88 Clarke electrolyte liquid volume

metallurgical 88 model 161

Aqueous infinite dilution heat Clausius-Clapeyron equation for

capacity model 176 heat of vaporization 159

Aspen Liquid Mixture Viscosity 212 Coal property models 257

model 212 Constant activity coefficient model

Aspen polynomial equation 174 88

COSMO-SAC solvation model 88

B COSTALD liquid volume model 164

Criss-Cobble aqueous infinite

Barin equations thermodynamic

dilution ionic heat capacity

property model 190

model 177

Benedict-Webb-Rubin-Starling 17

property model 17

Braun K-10 model 152 D

Brelvi-O'Connell model 161 Dawson-Khoury-Kobayashi

Bromley-Pitzer activity coefficient diffusion model 244

model 83 binary 244

BWR-Lee-Starling property model mixture 244

16 DCOALIGT coal density model 266

Dean-Stiel pressure correction

C viscosity model 222

Debye-Huckel volume model 165

Cavett thermodynamic property

DGHARIGT char density model 266

model 190

Diffusivity models list 242

Chao-Seader fugacity model 153

DIPPR 7

Chapman-Enskog 213, 216, 242,

equations 7

243

280 Index

DIPPR model 156, 167, 181, 207, G

213, 233, 237, 249

General models for

heat of vaporization 156

nonconventional components

ideal gas heat capacity 181

255, 256, 260

liquid surface tension 249

coal model for enthalpy 260

liquid thermal conductivity 233

density polynomial model 256

liquid volume 167

enthalpy and density models list

surface tension 249

255

vapor thermal conductivity 237

heat capacity polynomial model

vapor viscosity 213

256

viscosity 207, 213

Grayson-Streed fugacity model 153

DIPPR/IK-CAPE model 177

Group contribution activity

liquid heat capacity 177

coefficient models 137, 139,

DNSTYGEN nonconventional

140

component density model 256

Dortmund-modified UNIFAC 139

Lyngby-modified UNIFAC 140

E UNIFAC 137

Electrolyte models 161, 193, 194,

223, 232, 245, 253 H

Clarke liquid volume 161

Hakim-Steinberg-Stiel/DIPPR

electrolyte NRTL enthalpy 193

surface tension 249

Gibbs energy 194

Hansen solubility parameter model

Jones-Dole viscosity 223

109

Nernst-Hartley diffusion 245

Hayden-O'Connell 20

Onsager-Samaras surface

property model 20

tension 253

HCOALGEN general coal model for

Riedel thermal conductivity 232

enthalpy 260

Electrolyte NRTL 91, 193, 194

Heat capacity models list 176

activity coefficient model 91

Heat of vaporization 156

enthalpy thermodynamic

model 156

property model 193

Helgeson thermodynamic property

Gibbs energy thermodynamic

model 201

property model 194

Henry's constant solubility

eNRTL-SAC activity coefficient

correlation model 187

model 104

HF equation of state 22

Enthalpies model based on

property model 22

different reference states 196

Huron-Vidal mixing rules 76

Enthalpy and density models for

coal and char 257

ENTHGEN nonconventional I

component heat capacity IAPS models for water 222, 231,

model 256 249

Equation-of-state 14 surface tension 249

property models 14 thermal conductivity 231

extrapolation 9 viscosity 222

Ideal gas law 26

F property model 26

Ideal gas/DIPPR heat capacity

Fugacity models list 147

model 181

Ideal liquid activity coefficient

model 110

IGT density model for 266

Index 281

char 266 property model 91

coal 266 NRTL-SAC 116

Using 121

J

O

Jones-Dole electrolyte correction

viscosity model 223 Onsager-Samaras electrolyte

surface tension model 253

K option codes

activity coefficient models 269

Kent-Eisenberg fugacity model 154 enthalpy models 276

equation of state models 271

L gibbs energy models 278

soave-redlich-kwong models 274

Lee-Kesler Plöcker property model

transport property models 268

28

Lee-Kesler property model 26

Letsou-Stiel viscosity model 225 P

Li mixing rule thermal conductivity Peng-Robinson 44, 46, 48, 66

model 232 alpha functions 66

Liquid Constant Molar Volume MHV2 property model 48

Model 166 property model 46

Liquid enthalpy 196 Wong-Sandler property model 48

thermodynamic property model Physical properties 11, 14

196 models 11, 14

Lucas vapor viscosity model 225 Pitzer activity coefficient model 122

Polynomial activity coefficient

M model 133

PPDS Heat of Vaporization

Mathias alpha function 70

Equation 157

Mathias-Copeman alpha function

PPDS Liquid Heat Capacity 179

66, 70

Predictive Soave-Redlich-Kwong-

Maxwell-Bonnell vapor pressure

Gmehling mixing rules 79

model 155

Predictive SRK property model

MHV2 mixing rules 78

(PSRK) 48

Modified MacLeod-Sugden surface

Property models 5, 11, 14

tension model 254

equation-of-state list 14

Modified Rackett model for molar

list of 5

volume 173

thermodynamic list 11

Molar volume and density models

PSRK 48

list 159

property model 48

N

R

Nernst-Hartley electrolyte diffusion

Rackett mixture liquid volume

model 245

model 171

Nonconventional solid property

Rackett/DIPPR pure component

models 255

liquid volume model 167

density 255

Redlich-Kister activity coefficient

enthalpy 255

model 135

list of 255

Redlich-Kwong 49, 70

Nothnagel 30

alpha function 70

property model 30

property model 49

NRTL 91

282 Index

Redlich-Kwong-Aspen property mixtures 248

model 49 models list 248

Redlich-Kwong-Soave 52, 54, 56, Modified MacLeod-Sugden 254

70

alpha function equations 70 T

alpha function list 70

Boston-Mathias property model Thermal conductivity 229, 236

52 models list 229

MHV2 property model 54 solids 236

Soave-Redlich-Kwong property thermo switch 7

model 56 Thermodynamic property 11, 190

Wong-Sandler property model 54 list of additional models 190

Redlich-Kwong-Soave property models list 11

model 50 Three-suffix Margules activity

Riedel electrolyte correction coefficient model 136

thermal conductivity model THRSWT 7

232 Transport property 204

models list 204

transport switch 7

S

TRAPP 227, 240

Sato-Riedel/DIPPR thermal thermal conductivity model 240

conductivity model 233 viscosity model 227

Scatchard-Hildebrand activity TRNSWT 7

coefficient model 135 Twu Liquid Viscosity 227

Schwartzentruber-Renon property

model 54 U

Soave-Redlich-Kwong property

model 56 UNIFAC 137, 139, 140

Solid Antoine vapor pressure activity coefficient model 137

models 155 Dortmund modified activity

Solid Thermal Conductivity coefficient model 139

Polynomial 236 Lyngby modified activity

Solids polynomial heat capacity coefficient model 140

model 185 UNIQUAC 141

Solubility correlation models 187 activity coefficient model 141

list 187 Units for Temperature-Dependent

SRK-Kabadi-Danner property Properties 6

model 58

SRK-ML property model 60 V

Standard Peng-Robinson property

Van Laar activity coefficient model

model 46

143

Standard Redlich-Kwong-Soave

Vapor pressure model list 147

property model 50

Viscosity 206

Steam tables 15, 29

models 206

NBS/NRC 29

property models 15

STEAMNBS property method 29 W

Stiel-Thodos pressure correction Wagner Interaction Parameter

thermal conductivity model activity coefficient model 144

239 Wagner vapor pressure model 147

Stiel-Thodos/DIPPR thermal Wassiljewa-Mason-Saxena mixing

conductivity model 237 rule for thermal conductivity

Surface tension 248, 254 241

Index 283

Water solubility model 188

Watson equation for heat of

vaporization 157

Wilke-Chang diffusion model 246,

247

binary 246

mixture 247

WILS-GLR property method 196

WILS-LR property method 196

Wilson (liquid molar volume)

activity coefficient model 146

Wilson activity coefficient model

145

Wong-Sandler mixing rules 81

284 Index